Computations at the CASPT2, CBS-QB3, and B3LYP levels of theory demonstrate that β-substitution of vinyl cations with π-donors switches the ground state of these ions from the familiar closed-shell singlet state to a carbene-like triplet state similar to the electronic state of triplet phenyl cations. Although the parent vinyl cation is a ground-state singlet species with a very large energy gap to the lowest energy triplet state, substituting the β hydrogens with just one strong π-donor (e.g., NH2, NMe2, OMe) or two moderate π-donors (e.g., F, OH, Ar, vinyl) makes the triplet state the computed ground electronic state. In many cases, the singlet states for these β π-donor-substituted vinyl cations are prone to rearrangements, although such rearrangements can be inhibited through incorporation of the π-donors into rings. For example, a vinyl cation based on 1,3-dimethyl-2-methylene imidazolidine (32) is predicted to show a substantial barrier to singlet state rearrangement as well as possess a triplet ground state with a large energy gap. In contrast to the singlet states, the stabilized triplet states appear to be well behaved and more immune to rearrangements. These triplet ions may exhibit substantially different properties and reaction chemistry than those seen for typical closed-shell vinyl cations.