Abstract: The porphyrins as photoelectrodes in the photovoltaic cells of liquid junction type have been studied.In this paper, the adsorption isotherm of anion-surfactants at the solid surface, has been used to analyze the correlation between the ion concentration logarithmic function and the increase of photovoltaic effect. The influence of alkyl chain length, polar head group, cationic surfactants and non-ionic surfactants on the enhanced photovoltaic effect has also been studied. It has been shown that the effect of the structure of inner Helmholtz layer and the change of parameters on the photovotaic effect plays an important role in the photovoltaic cell.