Chalcogenirenium cations, featuring an unsaturated three‐membered organic ring, are limited but known to be synthesizable from alkynes with bulky electron‐donating groups. Metalla‐chalcogenirenium compounds have been synthesized as stable compounds through the reactions of a cyclic metal‐carbyne complex—metallapentalyne with PhSCl, PhSeCl or PhTeCl. As a result of the high strain in the three‐membered metallacycles, the metalla‐chalcogenirenium cations react readily with the base or chloride ions. These reactions furnish a series of unprecedented chalcogenirenium cations with intact M=C bonds. The intrinsic stabilization effect of aromaticity is further elucidated by density functional calculations.