Conventional photoelectrochemical (PEC) cells are based on planar photoelectrodes supported on glass substrates and liquid electrolytes. Only few recent studies have examined an alternative PEC design which is robust and scalable, where the key elements are polymeric electrolyte membranes and porous photoelectrodes. This work aims to give further insights on the operation of such cells utilizing titania photoelectrodes and proton and hydroxide ion conducting membranes. Two families of photoelectrodes were developed on Ti porous substrate; TiO2 nanotubes grown by anodization and subsequent oxygen annealing, and TiO2 layers developed under oxygen annealing. Initial screening of the photoanodes for water splitting and (poly)alcohol photo-oxidation took place in conventional PEC cells. We found that the annealing temperature affects the performance of the photoanodes, evidenced by a monotonic increase in the activity for water photo-oxidation with increasing annealing temperature. Moreover it was demonstrated that anatase phase is predominantly active for the (poly) alcohol electro-oxidation, while there is a synergy between rutile and anatase which is beneficial for water splitting. In addition, the most promising photoanodes for water splitting were evaluated in our polymeric electrolyte membrane photoelectrochemical(PEM-PEC) cell during gas phase operation. It was found that PEM-PEC operation is more efficient when OH- conducting membranes are used, while the nature of the carrier gas does not significantly influence the activity. Overall, PEM-PEC operation is more promising than conventional PEC in both acidic and alkaline media, since comparable (or even at some cases higher) photocurrents were obtained while liquid pumping systems are not required for PEM-PEC devices.