The substituent effect of electron‐withdrawing groups on electron affinity and gas‐phase basicity has been investigated for substituted propargyl radicals and their corresponding anions. It is shown that when a hydrogen of the α‐CH2 group or acetylenic CH in the propargyl system is substituted by an electron‐withdrawing substituent, electron affinity increases, whereas gas‐phase basicity decreases. The calculated electron affinities are 0.95 eV (CHCCH2•), 1.15 eV (CHCCHF•), 1.38 eV (CHCCHCl•), 1.48 eV (CHCCHBr•) for the isomers with terminal CH and 1.66 eV (CFCCH2•), 1.70 eV (CClCCH2•), 1.86 eV (CBrCCH2•) for the isomers with terminal CX at B3LYP level. The calculated gas‐phase basicities for their anions are 378.4 kcal/mol (CHCCH2:−), 371.6 kcal/mol (CHCCHF:−), 365.1 kcal/mol (CHCCHCl:−), 363.5 kcal/mol (CHCCHBr:−) for the isomers with terminal CH and 362.6 kcal/mol (CFCCH2:−), 360.4 kcal/mol (CClCCH2:−), 356.3 kcal/mol (CBrCCH2:−) for the isomers with terminal CX at B3LYP level. It is concluded that the larger the magnitude of electron‐withdrawing, the greater is the electron affinity of radical and the smaller is the gas‐phase basicity of its anion. This tendency of the electron affinities and gas‐phase bacisities is greater in isomers with the terminal CX than isomers with the terminal CH. Copyright © 2009 John Wiley & Sons, Ltd.