Pyroelectricity (from Greek: pyr (πυρ), "fire" and electricity) is a property of certain crystals which are naturally electrically polarized and as a result contain large electric fields. Pyroelectricity can be described as the ability of certain materials to generate a temporary voltage when they are heated or cooled. The change in temperature modifies the positions of the atoms slightly within the crystal structure, so that the polarization of the material changes. This polarization change gives rise to a voltage across the crystal. If the temperature stays constant at its new value, the pyroelectric voltage gradually disappears due to leakage current. The leakage can be due to electrons moving through the crystal, ions moving through the air, or current leaking through a voltmeter attached across the crystal.

Pyroelectric charge in minerals develops on the opposite faces of asymmetric crystals. The direction in which the propagation of the charge tends is usually constant throughout a pyroelectric material, but, in some materials, this direction can be changed by a nearby electric field. These materials are said to exhibit ferroelectricity.

All known pyroelectric materials are also piezoelectric. Despite being pyroelectric, novel materials such as boron aluminum nitride (BAlN) and boron gallium nitride (BGaN) have zero piezoelectric response for strain along the c-axis at certain compositions, the two properties being closely related. However, note that some piezoelectric materials have a crystal symmetry that does not allow pyroelectricity.

Pyroelectric materials are mostly hard and crystals; however, soft pyroelectricity can be achieved by using electrets.

Pyroelectricity is measured as the change in net polarization (a vector) proportional to a change in temperature. The total pyroelectric coefficient measured at constant stress is the sum of the pyroelectric coefficients at constant strain (primary pyroelectric effect) and the piezoelectric contribution from thermal expansion (secondary pyroelectric effect). Under normal circumstances, even polar materials do not display a net dipole moment. As a consequence, there are no electric dipole equivalents of bar magnets because the intrinsic dipole moment is neutralized by "free" electric charge that builds up on the surface by internal conduction or from the ambient atmosphere. Polar crystals only reveal their nature when perturbed in some fashion that momentarily upsets the balance with the compensating surface charge.

Spontaneous polarization is temperature dependent, so a good perturbation probe is a change in temperature which induces a flow of charge to and from the surfaces. This is the pyroelectric effect. All polar crystals are pyroelectric, so the 10 polar crystal classes are sometimes referred to as the pyroelectric classes. Pyroelectric materials can be used as infrared and millimeter wavelength radiation detectors.

An electret is the electrical equivalent of a permanent magnet.

The pyroelectric coefficient may be described as the change in the spontaneous polarization vector with temperature: $${\displaystyle p_{i}={\frac {\partial P_{S,i}}{\partial T}}}$$ where p_i (Cm⁻²K⁻¹) is the vector for the pyroelectric coefficient.