In this study peripherally tetra-substituted metal-free, metallophthalocyanines bearing (3,4-dimethoxybenzyl) oxy groups have been synthesized and characterized. Electrochemical properties of novel phthalocyanines 4, 5, 6, and 7 were determined by cyclic and square wave voltammetry in order to define their possible applications in different electrochemical technologies. Co-II and (TiO)-O-IV metal ions behave as redox active cations in the core of the CoPc and TiOPc complexes, respectively. Voltammetric studies revealed that phthalocyanines have reversible/irreversible redox processes, which are the main requirement for the technological usage of these compounds.