This study investigates the charge injection barrier at the phthalocyanine (H2Pc)/Pd using accumulated charge measurement (ACM). Because the hole injection barrier is relatively small, the voltage oscillation method in ACM is achieved at the highest occupied molecular orbital/Pd interface, and the hole injection barrier was determined to be 0.26 eV. A negative offset voltage was applied to determine the electron injection barrier at the lowest unoccupied molecular orbital (LUMO)/Pd interface. However, when the electron injection barrier was significantly large, the charge-injected thermal equilibrium state (CITES) could not be achieved at the interface, and an accurate injection barrier could not be determined. Surprisingly, by applying a positive offset voltage, a CITES of electrons was obtained at the LUMO/Pd interface, and the band gap was determined to be 2.75 eV. Furthermore, the electron injection barrier was found to be 2.49 eV. By applying a positive offset voltage, band bending occurred at the H2Pc/Pd interface, thereby reducing the depletion layer in the LUMO and enabling the determination of the band gap and electron injection barrier.