The ion-ion neutralization reactions of He+ with C6F5X- (X=F, Cl, Br, CF3) leading to He* have been spectroscopically studied in a helium flowing afterglow. Although both singlet and triplet He* states were formed when X=F and Cl, only triplet He* states were produced when X=Br and CF3. More than 99% of the product He* atoms were formed in the low-lying He(3s, 3p, or 3d) states for all the reactions, and their electronic-state distributions were similar. The electronic-state populations decreased rapidly with increasing excitation energy of He*. They were represented by effective electronic temperatures of 0.070-0.19 eV. The observed electronic-state distributions were compared with those predicted from a simple statistical theory.