We present a joint experimental and theoretical study on the desolvation of Ba+ cations in 4He nanodroplets excited via the 6p 6s transition. The experiments reveal an efficient desolvation process yielding mainly bare Ba+ cations and Ba+Hen exciplexes with n = 1 and 2. The speed distributions of the ions are well described by a Maxwell-Boltzmann distributions with temperatures ranging from 60 to 178 K depending on the excitation frequency and Ba+Hen exciplex size. These results have been analyzed by calculations based on a time-dependent density functional description for the helium droplet combined with classical dynamics for the Ba+. In agreement with experiment, the calculations reveal the dynamical formation of exciplexes following excitation of the Ba+ cation. In contrast to experimental observation, the calculations do not reveal desolvation of excited Ba+ cations or exciplexes, even when relaxation pathways to lower lying states are included.