In this paper, the presence of hydrogen bonding in chloroform-acrylate polymer mixtures was demonstrated by observation of H-1 and C-13 NMR chemical shifts. Comparison of the NMR chemical shifts in polymer solutions with their low molecular weight analogues showed the effect of steric hindrance on hydrogen bonding. Using the data obtained by NMR analysis, this work correlates the proton chemical shift with the fraction of associated hydrogen in chloroform, which is related to the polymer steric hindrance effect on molecular association. A lattice-fluid hydrogen bonding and equation of state (LFHB-EOS) model enables correct prediction of chloroform solubility in poly(acrylate)s due to the inclusion of hydrogen bonding and its equation of state nature. This initial investigation is helpful for understanding intermolecular;interaction for relatively weak hydrogen-bonded polymer solutions.