A review of past and present studies on orientation, rheology, and FTIR investigations on a hydrogen bond-forming polymer, poly(vinyl phenol) (PVPh), and its blends with polyethylene oxide (PEO), poly(methyl methacrylate) (PMMA), and poly(vinyl methyl ether) (PVME) is presented. Orientation is analyzed on the basis of deformation-induced orientation and relaxation. For deformation, it is proposed from recent molecular modeling studies that orientation is similar for flexible backbone polymers of the types studied. To investigate relaxation, dynamical rheology analysis was performed previously on PVPh/PEO blends and global molecular weight between entanglement, M-e, and chain friction zeta were estimated. M-e remained close to that of the polymer forming the dominant network, a discontinuity being observed near 50 mole percent. Friction coefficient exhibited a maximum near that of the orientation function of this system. Near-infrared measurements also showed a maximum in the number of interchain hydrogen bonds at this concentration, although broader than that of orientation or of the friction coefficient. For strongly interacting blends, it is proposed that a break in orientation behavior would be associated with the dominant network present, and therefore to M-e, whereas zeta will dictate whether orientation decreases or increases in a given network domain.