The thermodynamics and some vibrational properties of hydrogen-bonded complexes of methanol with 23 hydrogen-bond acceptors (HBAs) have been determined in CCl(4) by FTIR spectrometry. The experimental sample contains carbon, nitrogen, oxygen, sulfur, fluorine, and chlorine organic bases and covers an energetic range of 13 kJ mol(-1) in the basicity scale (-Delta G), 22 kJ mol(-1) in the affinity scale (-Delta H), and 400 cm(-1) in the spectroscopic scale (Delta v((OH))) (from benzene to trimethylphosphane oxide and amines). The experimental results in CCl(4) are compared to those computed in the gas phase at various levels of theory. Ninety five percent of the variance of the red shift and 89% of the variance of the intensification of the OH stretching upon hydrogen bonding are explained by gas-phase B3LYP/6-31+G(d,p) calculations. However, this level does not satisfactorily explain the thermodynamic properties. Only 68% of thevariance of the methanol affinity (-Delta H) is taken into account. MP2/aug-cc-pVTZ//B3LYP/6-31+G(d,p) affinity calculations raise the explanation to 77% for all HBAs and to 93% when three outliers (Me(2)SO, Me(3)PO, and tetrahydrothiophene) are excluded. Discrepancies are analyzed in terms of experimental errors, calculation approximations, and solvation.