Photolysis of the halfsandwich tetracarbonylmetal complexes CpV(CO)4, Cp*V(CO)4 and Cp*Ta(CO)4 in solution in the presence of di(organyl)dichalcogenides E2R2 (E = S, Se, Te; R = Me, Ph, Fc) leads to diamagnetic doubly organochalcogenolato‐bridged compounds, [Cp()M(CO)2(μ‐ER)]2. According to the X‐ray structure determinations carried out for [CpV(CO)2(μ‐TeMe)]2, [Cp*V(CO)2(μ‐TePh)]2 and [Cp*Ta(CO)2(μ‐SPh)]2, the molecular framework consists of a folded M2(μ‐ER)2 ring with the cyclopentadienyl ligands in cis‐configuration and the organyl substituents R in a syn‐equatorial arrangement, thus forming a bowl‐shaped molecule with the four terminal CO ligands protruding into the inner sphere. The M…M distances (in the range between 305 and 330 pm) are not considered to indicate direct bonding interactions. The vanadium complexes [Cp()V(CO)2(μ‐ER)]2 are completely decarbonylated in the presence of an excess of E2R2 in boiling toluene, and in many cases the paramagnetic quadruply‐bridged products, [CpV(μ‐ER)2]2, can be isolated.