Reaction of CHI3 with six equivalents of CrCl2 in THF at low temperatures affords [Cr3Cl3(μ2‐Cl)3(μ3‐CH)(thf)6] as the first isolable high‐yield CrIII μ3‐methylidyne complex. Substitution of the terminal chlorido ligands via salt metathesis with alkali‐metal cyclopentadienides generates isostructural half‐sandwich chromium(III)‐μ3‐methylidynes [CpR 3Cr3(μ2‐Cl)3(μ3‐CH)] (CpR=C5H5, C5Me5, C5H4SiMe3). Side and decomposition products of the Cl/CpR exchange reactions were identified and structurally characterized for [Cr4(μ2‐Cl)4(μ2‐I)2(μ4‐O)(thf)4] and [(η5‐C5H4SiMe3)CrCl(μ2‐Cl)2Li(thf)2]. The Cl/CpR exchange drastically changed the ambient‐temperature effective magnetic moment μ eff from 9.30/9.11 μ B (solution/solid) to 3.63/4.32 μ B (CpR=C5Me5). Reactions of [Cr3Cl3(μ2‐Cl)3(μ3‐CH)(thf)6] with aldehydes and ketones produce intricate mixtures of species through oxy/methylidyne exchange, which were partially identified as radical recombination products through GC/MS analysis and 1H NMR spectroscopy.