The optical properties of zinc phthalocyanine ((ZnPc)-Pc-II) and magnesium phthalocyanine ((MgPc)-Pc-II) in DMSO and DMF solutions have been extensively investigated, and the photoelectrochemical behaviors of layer-by-layer hybrid junctions formed of the two metallo(II) phthalocyanines (M(II)Pcs) and wide-band-gap colloidal semiconductors, namely, ZnO and TiO2 nanocrystals (NCs), have been probed. Different experimental conditions, such as the Pc center metal ion, dye concentration, and solvent identity, were investigated in order to elucidate their effects on the photoelectrochemical performances of the prepared heterojunctions. Finally, thermal treatment of either dye and NC films and control of the NC shape and surface chemistry were also studied and, interestingly, were found to be critical in affecting the performance of photochemical sensitization processes, occurring at the dye/oxide and oxide/solution interfaces.