The miscibility and morphology of poly(caprolactone) (PCL) and poly (4-vinylphenol) (PVPh) blends were investigated by using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and C-13 solid state nuclear magnetic resonance (NMR) spectroscopy. The DSC results indicate that PCL is miscible with PVPh. FTIR studies reveal that hydrogen bonding exists between the hydroxyl groups of PVPh and the carbonyl groups of PCL. C-13 cross polarization (CP)/magic angle spinning (MAS)/dipolar decoupling (DD) spectra of the blends show a 1 ppm downfield shifting of C-13 resonance of PVPh hydroxyl-substituted carbons and PCL carbonyl carbons with increasing PCL content. Both FITR and NMR give evidence of inter-molecular hydrogen bonding within the blends. The proton spin-lattice relaxation in the laboratory frame, T-1(H), and in the rotating frame, T-1p(H), were studied as a function of the blend composition. The T-1(H) results are in good agreement with thermal analysis; i.e. the blends are completely homogeneous on the scale of 50-80 nm. The T-1p(H) results indicate that PCL in the blends has both crystalline and amorphous phases. The amorphous PCL phase is miscible with PVPh, but the PCL crystal domain size is probably larger than the spin-diffusion path length within the T-1p(H) time-frame, i.e. larger than 2-4 nm. The mobility differences between the crystalline and amorphous phases of PCL are clearly visible from the T-1p(H) data.