A "photoelectrochemical cell" is one of two distinct classes of device. The first produces electrical energy similarly to a dye-sensitized photovoltaic cell, which meets the standard definition of a photovoltaic cell. The second is a photoelectrolytic cell, that is, a device which uses light incident on a photosensitizer, semiconductor, or aqueous metal immersed in an electrolytic solution to directly cause a chemical reaction, for example to produce hydrogen via the electrolysis of water.
Both types of device are varieties of solar cell, in that a photoelectrochemical cell's function is to use the photoelectric effect (or, very similarly, the photovoltaic effect) to convert electromagnetic radiation (typically sunlight) either directly into electrical power, or into something which can itself be easily used to produce electrical power (hydrogen, for example, can be burned to create electrical power, see photohydrogen).
The standard photovoltaic effect, as operating in standard photovoltaic cells, involves the excitation of negative charge carriers (electrons) within a semiconductor medium, and it is negative charge carriers (free electrons) which are ultimately extracted to produce power. The classification of photoelectrochemical cells which includes Grätzel cells meets this narrow definition, albeit the charge carriers are often excitonic.
The situation within a photoelectrolytic cell, on the other hand, is quite different. For example, in a water-splitting photoelectrochemical cell, the excitation, by light, of an electron in a semiconductor leaves a hole which "draws" an electron from a neighboring water molecule:
H2O(l) + [hv] + 2h+ -> 2H+ (aq) + 1/2O2(g)
This leaves positive charge carriers (protons, that is, H+ ions) in solution, which must then bond with one other proton and combine with two electrons in order to form hydrogen gas, according to:
2H+ + 2e- -> H2(g)
A photosynthetic cell is another form of photoelectrolytic cell, with the output in that case being carbohydrates instead of molecular hydrogen.