Experimental product ratios in ozonolyses of alkyl vinyl ethers in solution do not fit with expectations from statistical rate theories. The selectivity among cleavage pathways increases with the size of the alkyl group but to an extent that is far less than RRKM theory would predict. Trajectory studies account for the observed selectivities and support a mechanism involving a competition between cleavage of the primary ozonide and intramolecular vibrational energy redistribution. An approximate statistical model is presented that assumes that RRKM theory holds for a molecular subset of the primary ozonides, allowing estimates of the rates of energy loss from the primary ozonides based on the observed product ratios.