Cadmium sulfide (CdS) has been employed as an alternative acceptor for planar heterojunction solar cell based on copper phthalocyanine (CuPc). Spin-coated poly-3,4-ethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS) on indium tin oxide (ITO)-coated glass substrates was used for the vacuum deposition of CuPc and CdS planar heterojunction. In the present study, we have fabricated two different architectures of CuPc/CdS devices: (1) ITO/PEDOT:PSS/CuPc/CdS/Al and (2) ITO/PEDOT:PSS/CuPc/CdS/LiF/Al. Our results indicate that the CdS could effectively facilitate charge transport in the nanostructured network, and be a good acceptor. The fabricated bare CuPc/CdS device shows 0.13 % conversion efficiency while incorporation of LiF layer between CuPc/CdS and Al contact facilitates low-recombination rate results similar to 43 % enhancement in efficiency. The ITO/PEDOT:PSS/CuPc/CdS/LiF/Al device shows 0.30 % power conversion efficiency.