The intercalation compounds Li 0.96 (H 2 O) 0.77 (PEO) 0.63 Ni 0.48 PS 3 and Li 0.94 (H 2 O) 0.92 (PEO) 0.94 Fe 0.48 PS 3 obtained by the insertion of PEO in MPS 3 form lithium-polyethylene oxide complexes containing Li + exchangeable cation in the interlayer space. Polyethylene oxide (PEO) is able to associate interlayer cation increasing the ionic conductivity of NiPS 3 and FePS 3. These compounds constitute a new family of intercalates MPS 3 (M=Ni, Fe) host-layer materials.The new materials were characterized by powder X-Ray diffraction (XRD), Fourier-transformed infrared (FT-IR), differential thermal and thermogravimetric analyses (DTA/TG), energy dispersive X-Ray (EDX), inductively coupled plasma (ICP) and electrochemical impedance measurements. The intercalation compound Li 0.96 (H 2 O) 0.77 (PEO) 0.63 Ni 0.48 PS 3 shows an ionic conductivity of 0.13μS/cm, and dc electronic conductivity of ca. 0.1μS/cm which is twice that of NiPS 3 .