Studies of CuPc thin films on underlying ferroelectric copolymeric and terpolymeric substrates have been performed by ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Work function (WF) and highest occupied molecular orbital (HOMO) energy level shift observed from UPS spectroscopy for successive deposition of CuPc molecules on ferroelectric polymer surfaces confirm the formation of interface dipole at the CuPc-ferroelectric polymer interface owing to charge transfer from the tailing region of the CuPc HOMO density of states (DOS) to the ferroelectric polymer layer. According to our thickness dependent XPS data, CuPc molecules are coupled to the organic ferroelectric surfaces through the central metal atom of the CuPc molecules, i.e., copper atom, and the halogens of underlying ferroelectric polymer surfaces, and hence support the charge transfer phenomenon from CuPc molecules to the ferroelectric polymer substrate. Polarization dependent NEXAFS results reveal that CuPc molecules retain their tilted geometrical configuration even at submonolayer thickness of the molecular films on both ferroelectric surfaces and confirms the electronic structural disturbance associated with structural modification of CuPc molecules due to interfacial charge transfer. Therefore, the energy level alignment with increment in the thickness of CuPc films at both the organic semiconductor-ferroelectric polymer interface is controlled by the charge transfer phenomenon from deposited CuPc molecules to the organic ferroelectric substrates. Our results provide a clear understanding about chemical interactions, molecular configurations, energy level alignment, and their correlation at CuPc/polymeric ferroelectric interfaces that can be important for organic nonvolatile memory and synaptic based thin-film transistor devices.