Numerous transition metal compounds can be added to poly(vinyl chloride) to decrease the smoke evolved during burning or smoldering conditions. Model compound pyrolysis experiments have been carried out to investigated the mechanisms by which smoke retarder additives function in PVC. Three models were used: 3‐chloropentane, 2,4‐dichloropentane, and 2,4,6‐trichlorohenptane. The additives MoMO3 and Cu2O both enhanced the rate of dehydrochlorination and promoted the formation of crosslinked products (oligomers) during model compound pyrolysis, but their mechanistic pathways were found to be different. The choice of model compounds also was an important influence in determining the observed decomposition pathways. While much of the pyrolysis chemistry can be explained by Lewis acid catalysis, other effects also appear to be important. The pyrolysis results are interpreted in terms of an “early crosslinking” mechanism of smoke retardation in PVC. In this mechanism the metal smoke retarder works primarily by catalytically promoting early crosslinking of decomposing PVC chains to yield char as a residue.