Inverse vulcanization utilizes an organic compound as reagent for crosslinking elemental sulfur to result in corresponding polymeric material with a high sulfur content. This work, employing 1,3,5‐triisopropylbenzene (TIPB) as the reagent, demonstrates the first attempt on extending the scope of crosslinking agents of inverse vulcanization to saturate compounds. Under nuclear magnetic spectroscopic analysis, the reactions between TIPB and elemental sulfur take places through ring‐opening reaction of S8 resulting in sulfur radicals at sulfur chain ends, radicals transferring to isopropyl groups of TIPB, and radical coupling reactions between carbon radicals and sulfur radicals. The obtained products are similar to the sulfur polymers from conventional inverse vulcanization processes and show self‐healing property. This work demonstrates the first study on employing a saturate compound as the crosslinking agent for elemental sulfur through sequential radical transfer and coupling reactions in the “inverse vulcanization” processes. The sulfur‐rich polymers are similar to that from conventional inverse vulcanization agents. The scope of the reagents for inverse vulcanization has been successfully extended.