Equilibrium bindings of two low-molecular-weight hydrogen bond acceptor ligands, tetrahydrofuran (THF) and pyridine (PH), and their fully deuterated analogues TDF, PD) with poly(4-vinylphenol) (PVF) and its low-molecular-weight model, a hydrogen bond donor 4-isopropylphenol (IPP), were studied using spectroscopic (NMR) and theoretical (ab initio SCF-DFT B3LYP/6-31G(d)) methods as a first step of a general study of cooperative hydrogen bonding of H-bond-donating and -accepting macromolecules. Two reliable experimental methods of measuring the fraction of H-bonded or free ligands, which can be used as an indirect tool in further studies of macromolecular cooperative binding, were devised and examined in this study. The methods are complementary and independent. They are based on one hand on H-2 quadrupolar or H-1 longitudinal NMR relaxation and, on the other hand, on H-2 or H-1 PFG NMR self-diffusion measurement, using the pulsed-field-gradient spin-echo (PGSE) and pulsed-field-gradient stimulated echo (PGSTE) methods. It was shown that both the relaxation and PFG methods need viscosity correction using as an internal standard a relatively inert compound of a relaxation/diffusion rate similar to that of the internal standard (CDCl3 or HMDSO in the present case). After such normalization, the reliability of both methods was checked by calculating the equilibrium constants K of binding under a variety of ligand/donor ratios beta. Excepting the rather impractical region of low beta values, where cooperative self-association of the H-donating polymer takes place, both methods were found to be reasonably reliable. A slight anomaly in the relaxation behavior of pyridine and its stronger-than-expected binding to PVF was plausibly explained (using high-precision quantum mechanical calculations) by additional formation of weak C-H... O bonds to the neighboring units.