While transition metals are well known for assuming the formal oxidation state of zero in various compounds main group elements have rarely engaged in this practice. Recent reports of N-heterocyclic carbene-stabilized main group diatomic allotropes (i.e., Si₂, Ge₂, P₂, As₂) denote a breakthrough of zero-oxidation state main group chemistry. This Perspective addresses the synthesis and characterization of these highly reactive main group molecules, with a particular emphasis on the very recent progress in the reactivity study of carbene-stabilized Si₂ and P₂.