An efficient C–H bond functionalization of benzoxazoles with chromium(0) Fischer carbene complexes under catalyst-free conditions has been developed. A series of benzoxazoles and chromium(0) carbene complexes are compatible with the reaction. This transformation provides an alternative way for C–H bond alkylation of benzoxazoles. In the reaction mechanism the elimination of the Cr(CO)5 fragment seems more favored than the elimination of an alkoxy group, which is in sharp contrast to the previous reports on the reaction of organolithium reagents with chromium(0) Fischer carbene complexes.