This letter reports experimental results for the influence of target excitation and orbital alignment on the electron transfer process for the He⁺-Na(3s,3p) collision. The impact energy range is 1-15 keV in which the electron transfer cross sections have their maximum values. The total cross section parameters are found to depend sensitively on collision velocity. Disagreement is significant with recent theoretical 12 and 16 mo state predictions of Mo and Riera, and Dutta et al.