Accurate benchmark calculations of gas-phase basicities of small molecules are presented and compared with available experimental results. The optimized geometries and thermochemical analyses were obtained from MP2/aug-cc-pVTZ calculations. Two different ab initio electron-correlated methods MP2 and CCSD(T) were employed for subsequent gas-phase basicity calculations, and the single-point energies were extrapolated to the complete basis set (CBS) limit. The overall accuracy for different ab initio methods is compared, and the accuracy in descending order is CCSD(T)_CBS > CCSD(T)/aug-cc-pVDZ > (MP2/aug-ec-pVQZ approximate to MP2_CBS) > HF/aug-cc-pVQZ. The best root-mean-squared-error obtained was 1,0 kcal mol(-1) at the CCSD(T)_CBSHMP2/aug-cc-pVTZ level for a test set of 41 molecules. Clearly, accurate calculations for the electron correlation energy are important for the theoretical prediction of molecular gas-phase basicities. However, conformational effects were also found to be relevant in several instances when more complicated molecules were examined.