C-13 CP/MAS/DD (cross polarization/magic angle spinning/dipolar decoupling) NMR spectra and spin-lattice relaxation times T-1 were measured for highly crystalline stoichiometric complexes of poly(ethylene oxide) (PEO) with resorcinol, 2-methylresorcinol, hydroquinone, and p-nitrophenol. It was found that the hydrogen bonding between PEO and hydroxybenzene molecules in molecular complexes results in higher shielding (i.e., lower chemical shifts) of PEO carbons. The largest "upfield" shifts (similar to 2.5 ppm) were observed for PEO/p-nitrophenol and PEO/resorcinol complexes where the strongest hydrogen bonds exist, as shown by infrared spectra (OH stretching band). Hydrogen bonding is also the main reason for the lower mobility of PEO chains in molecular complexes with hydroxybenzenes, as detected by C-13 T-1 measurements. The very large rigidity of PEO chains in PEO/p-nitrophenol complexes is probably due also to other interactions (interaction of other functional groups of p-nitrophenol with PEG; pair dipolar interactions between p-nitrophenol molecules), in addition to hydrogen bonds.