AbstractThe classic pnictogen dichotomy stands for the great contrast between triply bonding very stable N2 molecules and its heavier congeners, which appear as dimers or oligomers. A banner example involves phosphorus as it occurs in nature as P4 instead of P2, given its weak π‐bonds or strong σ‐bonds. The P2 synthetic value has brought Lewis bases and metal coordination stabilization strategies. Herein, we discuss the unrealized encapsulation alternative using the well‐known fullerenes' capability to form endohedral and stabilize otherwise unstable molecules. We chose the most stable fullerene structures from Cn (n = 50, 60, 70, 80) and experimentally relevant from Cn (n = 90 and 100) to computationally study the thermodynamics and the geometrical consequences of encapsulating P2 inside the fullerene cages. Given the size differences between P2 and P4, we show that the fullerenes C70–C100 are suitable cages to side exclude P4 and host only one molecule of P2 with an intact triple bond. The thermodynamic analysis indicates that the process is favorable, overcoming the dimerization energy. Additionally, we have evaluated the host‐guest interaction to explain the origins of their stability using energy decomposition analysis.