We report on the facile conversion of [Pd2(μ-Cl)(μ-η3-R-allyl)(NHC)2] complexes, which are commonly considered undesirable off-cycle species in cross-coupling reactions, into active [PdCl(μ-Cl)(NHC)]2 pre-catalysts. All reactions proceed under mild conditions (40 °C, 1–2 hours in acetone) using inexpensive HCl as both an oxidant and chloride source. DFT calculations were performed to explore the possible mechanism of this transformation, which appears to involve a combination of two different pathways. Moreover this study provides insights into factors favoring and hindering Pd(I) dimer formation undesirable in catalysis.