Collisions of He(2'S) on atomic (He, Ar) or molecular (D2, 0,) targets are experimentally investigated at low keV energies (0.1-1.5 keV) by a time-of-flight technique. This method yields an overall picture of the various inelastic processes and their relative probabilities. Direct experimental evidence of the importance of the He(23P) and He(n'l') n ' s 3 excitations of the projectile with He and D, targets is reported. With an 0, target differential cross sections for He+ production measured at various energies reveal a rainbow feature. With the Ar target, the predominance of Penning ionisation and excitation transfer processes is confirmed. The experimental results concerning the He*-He system have been compared with the predictions of available theoretical models: the important He(2'P) production is qualitatively in agreement with calculations based on the c 'Xl-b' 'n, rotational coupling. The covalent-ionic transition in the He, molecule is proposed as a primary mechanism which can account for the Rydberg He(nl) population. For the other targets the possibility of connecting those Rydberg excitations with the existence of a transient ionic complex (He*-T-) is examined.