In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu4N+)2[MIVO(Pc4−)]2− (M=Ti, V) and (Bu3MeP+)2[MIVO(Pc4−)]2− (M=Ti, V) with [MIVO(Pc4−)]2− dianions were synthesized and characterized. Reduction of MIVO(Pc2−) carried out with an excess of sodium fluorenone ketyl in the presence of Bu4N+ or Bu3MeP+ is exclusive to the phthalocyanine centers, forming Pc4− species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand. The Pc negative charge increase caused the C−N(pyr) bonds to elongate and the C−N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn–Teller effects are significant in the [eg(π*)]2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q-bands were observed in the UV/Vis/NIR when MIVO(Pc2−) was reduced to [MIVO(Pc. 3−)]. − and [MIVO(Pc4−)]2−. From magnetic measurements, [TiIVO(Pc4−)]2− was found to be diamagnetic and (Bu4N+)2[VIVO(Pc4−)]2− and (Bu3MeP+)2[VIVO(Pc4−)]2− were found to have magnetic moments of 1.72–1.78 μB corresponding to an S=1/2 spin state owing to VIV electron spin. As a result, two latter salts show EPR signals with VIV hyperfine coupling.