Ferromagnetic metal-organic semiconductor (FM-OSC) hybrid interfaces have been shown to play an important role for spin injection in organic spintronics. Here, 11,11,12,12-tetracyanonaptho-2,6-quinodimethane (TNAP) is introduced as an interfacial layer in Co-OSCs heterojunctions with an aim to tune the spin injection. The Co/TNAP interface is investigated by use of X-ray and ultraviolet photoelectron spectroscopy (XPS/UPS), near edge X-ray absorption fine structure (NEXAFS) and X-ray magnetic circular dichroism (XMCD). Hybrid interface states (HIS) are observed at Co/TNAP interfaces, resulting from chemical interactions between Co and TNAP. The energy level alignment at the Co/TNAP/OSCs interface is also obtained, and a reduction of the hole injection barrier is demonstrated. XMCD results confirm sizeable spin polarization at the Co/TNAP hybrid interface.