In this paper, the interaction of poly(vinylidene fluoride) (PVDF) with single-walled carbon nanotubes (SWNTs) highly separated in metallic (M) and semiconducting (S) tubes is studied by resonant Raman scattering and FTIR spectroscopy. In this order, the PVDF/SWNTs membranes were prepared by the evaporation of dimethylformamide (DMF) from PVDF solutions containing i) the as-prepared SWNTs samples, i.e., as mixtures of metallic (33%) and semiconducting (66%) tubes (M + S-SWNTs), ii) SWNTs highly separated in metallic tubes (98%, M-SWNTs), and iii) SWNTs highly separated in semiconducting tubes (99%, S-SWNTs). An increase in the PVDF β phase weight, highlighted by the increase in the absorbance of IR band at 843 cm−1, is reported to take place in the presence of M + S-SWNTs and S-SWNTs. An increase of the PVDF γ crystalline phase weight is reported for the PVDF/M + S-SWNTs, PVDF/M-SWNTs and PVDF/S-SWNTs membranes. Using Raman scattering, a donor-acceptor interaction is invoked to take place at the interface PVDF/M + S-SWNTs and PVDF/S-SWNTs. In the case of the membranes based on PVDF and M-SWNTs, the changes reported in Raman spectra of the two constituents are explained on the base induction-interaction forces between the permanent dipole of PVDF and induced dipole of M-SWNTs.