In order to overcome the disadvantages of Li/SOCl2 battery, such as low voltage and small capacity, a series of phthalocyanine derivatives (MPcOc) as catalysts were added into the electrolyte. In this work, new phthalocyanines were synthesized by the microwave method, and this technique greatly shortened the reaction time. The catalysts were characterized by techniques including the FT-IR, UV–vis, ICP, SEM and XRD. The electrocatalytic performances of the MPcOc to Li/SOCl2 battery were evaluated by electrochemical testing. The synthesized catalysts showed excellent performance with the capacities increasing by 19.34–55.64%. Based on cyclic voltammetry measurements, the function of electrode surface and reaction mechanism were proposed.