Silacyclobutane was discovered to be an efficient C?H bond silylation reagent. Under the catalysis of RhI/TMS‐segphos, silacyclobutane undergoes sequential C?Si/C?H bond activations, affording a series of π‐conjugated siloles in high yields and regioselectivities. The catalytic cycle was proposed to involve a rarely documented endocyclic β‐hydride elimination of five‐membered metallacycles, which after reductive elimination gave rise to a Si?RhI species that is capable of C?H activation.