A potentiometer is an instrument for measuring voltage or 'potential difference' by comparison of an unknown voltage with a known reference voltage. If a sensitive indicating instrument is used, very little current is drawn from the source of the unknown voltage. Since the reference voltage can be produced from an accurately calibrated voltage divider, a potentiometer can provide high precision in measurement. The method was described by Johann Christian Poggendorff around 1841 and became a standard laboratory measuring technique.

In this arrangement, a fraction of a known voltage from a resistive slide wire is compared with an unknown voltage by means of a galvanometer. The sliding contact or wiper of the potentiometer is adjusted and the galvanometer briefly connected between the sliding contact and the unknown voltage. The deflection of the galvanometer is observed and the sliding tap adjusted until the galvanometer no longer deflects from zero. At that point the galvanometer draws no current from the unknown source, and the magnitude of voltage can be calculated from the position of the sliding contact.

This null balance measuring method is still important in electrical metrology and standards work and is also used in other areas of electronics.

Measurement potentiometers are divided into four main classes listed below.

The principle of a potentiometer is that the potential dropped across a segment of a wire of uniform cross-section carrying a constant current is directly proportional to its length. The potentiometer is a simple device used to measure the electrical potentials (or compare the e.m.f of a cell). One form of potentiometer is a uniform high-resistance wire attached to an insulating support, marked with a linear measuring scale. In use, an adjustable regulated voltage source E, of greater magnitude than the potential to be measured, is connected across the wire so as to pass a steady current through it.

Between the end of the wire and any point along it will be a potential proportional to the length of wire to that point. By comparing the potential at points along the wire with an unknown potential, the magnitude of the unknown potential can be determined. The instrument used for comparison must be sensitive, but need not be particularly well-calibrated or accurate so long as its deflection from zero position can be easily detected.

In this circuit, the ends of a uniform resistance wire R₁ are connected to a regulated DC supply V_S for use as a voltage divider. The potentiometer is first calibrated by positioning the wiper (arrow) at the spot on the R₁ wire that corresponds to the voltage of a standard cell so that ${\displaystyle {R_{2} \over R_{1}}={{\mbox{cell voltage}} \over V_{\mathrm {S} }}}$

A standard electrochemical cell is used whose emf is known (e.g. 1.0183 volts for a Weston standard cell).