The RhII-catalyzed decomposition of β,γ-unsaturated diazo ketones 1 in the presence of MeOH leads via vinylogous Wolff rearrangement to γ,δ-unsaturated esters 6 (Schemes 1 and 2). A modest asymmetric induction is achieved when the reaction is carried out with chiral tetrakis(pyrrolidinecarboxylato)- or tetrakis(oxazolidinonato)dirhodium(II) complexes. Vinyl and phenyl diazoacetates 11 and 20, respectively, or 1-diazo-3-phenyl-propan-2-one (25), when subjected to the same reaction conditions, react by OH insertion with MeOH (Schemes 3–5). In the absence of MeOH, phenyl diazoacetates 20 and 25 undergo intramolecular CH insertion to 22 and 26, respectively. Intramolecular CH insertion occurs with N-aryldiazoamides 23 even in the presence of MeOH (Scheme 5).