Novel photoelectrochemical processes are observed upon irradiation of the liquid|liquid|solid triple interface at microdroplets of N,N,N′,N′-tetrahexyl-para-phenylenediamine (THPD) deposited onto a basal plane pyrolytic graphite electrode and immersed in aqueous electrolyte solution. In the presence of neutral THPD, cathodic photo responses, and in the presence of THPD+, anodic photo responses with anion-dependent characteristics, are observed. A maximum in the photocurrents observed at intermediate coverage of the electrode surface suggests that the triple interface THPD|electrode|aqueous electrolyte is the reaction zone. This is the first report of photoelectrochemical processes at this type of interface.