To achieve highly efficient organic photovoltaics (OPVs), control of the molecular orientation is one of the prime important factors, for the interfacial dipole orientation and energy offset at the donor/acceptor (D/A) interface influence the device performance. We examine the effect of the planar-shape molecular orientation on the D/A interface, by comparing two different metal phthalocyanine molecules under identical process conditions. From the noticeable changes in the near edge X-ray absorption fine structure and ionization potential, copper phthalocyanine (CuPc) on a thin CuI layer reveals a strong change in molecular orientation compared to zinc phthalocyanine (ZnPc). To account for the different templating effect between CuPc and ZnPc, Cu d-d orbital coupling is evidenced as for the interaction between CuI and CuPc. The apparent change of the CuPc orientation reveals a relatively large energy offset at the CuPc/C-60 D/A interface and increased open-circuit voltage in the corresponding OPV device. The lying-down orientation of CuPc on CuI or face-on geometry at the C-60/CuPc interface induces strong electron-electron coupling and long-lived charge transfer exciton states, which is directly related to better charge separation and correspondingly good OPV performance.