Single-electron capture and ionization in He2++Na collisions at energies around the matching velocity (2–13 keV amu−1) have been studied both experimentally and theoretically. State-selective cross section for capture into the n = 2, 3, 4 and n ⩾ 5, and the ionization cross section as well as differential cross sections for capture into n = 3 and 4 were obtained by the MOTRIMS method and compared with CTMC calculations. Good agreement was found between experiment and CTMC, especially concerning capture into high n-shells (n = 4, n ⩾ 5) and the ionization cross sections. For capture into the subdominant n = 2 shell close coupling calculations show better agreement. The differential cross sections for capture into n = 3 and 4 show a different energy dependency.