The tricarbonylchromium complex of cyclopropa[b]naphthalene (3a) is deprotonated at C(1) with BuLi. Quenching of the resulting anion with Mel results in a 1:1 mixture of stereoisomeric methyl derivatives 6a and 6b. Peterson olefination of the bis‐silylated complex 3b affords the complexed alkylidenecycloproparene 5 in low yield. The tricarbonylchromium complex of cyclopropa[b]anthracene (10) is accessible via bis‐hydro‐desilylation of 9. Its X‐ray structure is also reported. All attempts to synthesize a tricarbonylchromium complex of benzocyclopropene (11a) failed.