It is shown that by adding small percentages of nonmesogenic compounds such as anthracene, rhodamine B or S (1% by weight) in the nematic 7A, in the smectic sitosteryl undecilenate and in sitosteryl octanoate or in the Compensated cholesteric mixtures cholesteryl chloride‐cholesteryl laurate 65:35% (by weight) and cholesteryl chloride‐cholesteryl myristate 63.63:36.37% (by weight), the mixtures exhibit photovoltaic effects. These effects are obtained only for the samples which are previously polarized under dc electric fields. Using continuous ultraviolet or visible light irradiation, values of 80 to 375 mV are obtained for the open‐circuit voltage.