Carbocations are traditionally thought to be closed-shell electrophiles featuring an empty orbital rich in p character. Here, density functional theory computations indicate that when strong π donors are not placed in direct conjugation with benzylic-type cations, alternative diradical configurations that resemble non-Kekulé diradicals are possible. For certain donor–acceptor frameworks, an open-shell singlet configuration is the computed ground state for the cation, whereas for coumarin and xanthenyl cations substituted with strong donors, a triplet diradical configuration is the computed ground state. Changing the substituent nature and attachment location substantially alters the energy gaps between the different electronic configurations and can manipulate the computed ground-state electronic configuration. There are few known examples of ground-state triplet carbocations, and, to our knowledge, no other examples of open-shell singlet carbocations. The open-shell singlet and triplet “carbocations” described here may have reactivity distinct from that of typical closed-shell singlet carbocations and, if appropriately stabilized, lead to organic materials with interesting electronic and magnetic properties.