A total of twenty four binuclear metal azaphthalocyanine compounds in four series of M2(azaPc)2Me, M2(azaPc)2SO2, M2(azaPc)2, M2(azaPc)2CO (M=Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) were synthesized by solid phase method, which were applied for Li/SOCl2 battery as electrocatalysts to enhance its capacity and discharge voltage. In all cases, the electrochemical performances of Li/SOCl2 batteries were improved compared with controls. It is worth mentioning that Mn2(azaPc)2SO2 increased the discharge voltage to 3.3485V, rising by 0.1570V compared with that of the blank. Co2(azaPc)2CO lengthened the discharge time to 1821s, rising by 75.80%. And Co2(azaPc)2 raised battery capacity to 35.24mAh, increasing by 79.56%. Based on cyclic voltammetry measurements, the reaction mechanism was found to involve an irreversible two-step electron transfer process and a hypothesis was conjectured. All the azaphthalocyanine compounds were characterized by element analysis, IR analysis, and UV-Vis absorption.