Non-stoichiometric compounds are chemical compounds, almost always solid inorganic compounds, having elemental composition whose proportions cannot be represented by a ratio of small natural numbers (i.e. an empirical formula); most often, in such materials, some small percentage of atoms are missing or too many atoms are packed into an otherwise perfect lattice work.^{[not verified in body]}

Contrary to earlier definitions, modern understanding of non-stoichiometric compounds view them as homogeneous, and not mixtures of stoichiometric chemical compounds.^{[not verified in body]} Since the solids are overall electrically neutral, the defect is compensated by a change in the charge of other atoms in the solid, either by changing their oxidation state, or by replacing them with atoms of different elements with a different charge. Many metal oxides and sulfides have non-stoichiometric examples; for example, stoichiometric iron(II) oxide, which is rare, has the formula FeO, whereas the more common material is nonstoichiometric, with the formula Fe_0.95O. The type of equilibrium defects in non-stoichiometric compounds can vary with attendant variation in bulk properties of the material. Non-stoichiometric compounds also exhibit special electrical or chemical properties because of the defects; for example, when atoms are missing, electrons can move through the solid more rapidly.^{[not verified in body]} Non-stoichiometric compounds have applications in ceramic and superconductive material and in electrochemical (i.e., battery) system designs.^{[citation needed]}

Nonstoichiometry is pervasive for metal oxides, especially when the metal is not in its highest oxidation state. For example, although wüstite (ferrous oxide) has an ideal (stoichiometric) formula FeO, the actual stoichiometry is closer to Fe_0.95O. The non-stoichiometry reflect the ease of oxidation of Fe²⁺ to Fe³⁺ effectively replacing a small portion of Fe²⁺ with two thirds their number of Fe³⁺. Thus for every three "missing" Fe²⁺ ions, the crystal contains two Fe³⁺ ions to balance the charge. The composition of a non-stoichiometric compound usually varies in a continuous manner over a narrow range. Thus, the formula for wüstite is written as Fe_1−xO, where x is a small number (0.05 in the previous example) representing the deviation from the "ideal" formula. Nonstoichiometry is especially important in solid, three-dimensional polymers that can tolerate mistakes. To some extent, entropy drives all solids to be non-stoichiometric. But for practical purposes, the term describes materials where the non-stoichiometry is measurable, usually at least 1% of the ideal composition.^{[citation needed]}

The monosulfides of the transition metals are often nonstoichiometric. Best known perhaps is nominally iron(II) sulfide (the mineral pyrrhotite) with a composition Fe_1−xS (x = 0 to 0.2). The rare stoichiometric FeS endmember is known as the mineral troilite. Pyrrhotite is remarkable in that it has numerous polytypes, i.e. crystalline forms differing in symmetry (monoclinic or hexagonal) and composition (Fe₇S₈, Fe₉S₁₀, Fe₁₁S₁₂ and others). These materials are always iron-deficient owing to the presence of lattice defects, namely iron vacancies. Despite those defects, the composition is usually expressed as a ratio of large numbers and the crystals symmetry is relatively high. This means the iron vacancies are not randomly scattered over the crystal, but form certain regular configurations. Those vacancies strongly affect the magnetic properties of pyrrhotite: the magnetism increases with the concentration of vacancies and is absent for the stoichiometric FeS.

Palladium hydride is a nonstoichiometric material of the approximate composition PdH_x (0.02 < x < 0.58). This solid conducts hydrogen by virtue of the mobility of the hydrogen atoms within the solid.^{[citation needed]}

It is sometimes difficult to determine if a material is non-stoichiometric or if the formula is best represented by large numbers. The oxides of tungsten illustrate this situation. Starting from the idealized material tungsten trioxide, one can generate a series of related materials that are slightly deficient in oxygen. These oxygen-deficient species can be described as WO_3−x, but in fact they are stoichiometric species with large unit cells with the formulas W_nO_3n−2, where n = 20, 24, 25, 40. Thus, the last species can be described with the stoichiometric formula W₄₀O₁₁₈, whereas the non-stoichiometric description WO_2.95 implies a more random distribution of oxide vacancies.^{[citation needed]}

At high temperatures (1000 °C), titanium sulfides present a series of non-stoichiometric compounds.

The coordination polymer Prussian blue, nominally Fe₇(CN)₁₈ and their analogs are well known to form in non-stoichiometric proportions. The non-stoichiometric phases exhibit useful properties vis-à-vis their ability to bind caesium and thallium ions.^{[citation needed]}