Two new axially or peripherally functionalized subphthalocyanines with the decoration of donoracceptor substituents have been successfully synthesized, characterized and employed in the application of resistive memory device via solution-processable technique. Axially substituted subphthalocyanine shows ternary resistive memory behavior with well-separated current ratios of 1:106:108 between OFF, ON1 and ON2 states, while only binary logic is observed for peripherally substituted subphthalocyanine. Computational studies show the presence of two well-separated charge transfer states in the axially substituted subphthalocyanine, while the charge transfer processes between the peripheral substituents and the subphthalocyanine core are found to be very close in energy. This work has demonstrated the impact of the substituent positioning on the subphthalocyanine-based memory device performance, providing a new research dimension for the future design and development of multistate organic resistive memory.