Metal-substituted phthalocyanine thin films such as copper-phthalocyanine (CuPc) are often used as photo-active and hole transporting layers (HTLs) in fully organic photovoltaic devices. In this work, CuPc is vacuum sublimated on an electron acceptor layer of mesoporous titania (TiO2) for the formation of hybrid TiO2:CuPc solar cell devices. The performance of these hybrid solar cell devices was demonstrated without and with dye sensitization at the TiO2:CuPc interface. The charge separation and photocurrent contribution at the interfaces in these multilayer hybrid devices was studied by using a variety of optoelectrical and photophysical characterization techniques. It is important to understand the fundamental interface properties of these multilayer hybrid solar cell devices for optimized performance.