The photocurrent vs potential characateristics for three different electrolyte—semiconductor junctions, representative of those generally found in semiconductor photoelectrochemistry, are analyzed in detail using parameters which define both the semiconductor and the electrolyte. It is shown that, in general, the behaviour of junctions including semiconductors with sufficiently wide energy pags and large free carriers densities, may be accurately described using the Gärtner model in the potential region which does not include the onset of the photocurrent. In this case, it is the characteristics of the semiconductor which control the photoresponse and the electrolyte does not induce limiting steps in the charge transfer across the interface. If certain restrictive conditions are fulfilled concerning the relative orders of magnitude of the semiconductor space charge region, diffusion length of minority carriers and penetration depth of light into the semiconductor, the value of the flat band potential may be easily determined by ploting i 2 ph vs V and extrapolating to i 2 ph = 0. In the other cases, the relation established by Gärtner between i ph and V has been verified provided that the free carriers density be sufficiently large.