CHF2Cl has been converted to CHF3 and CH4 as main products when hydrogenolyzed in the presence of RhCl3(Py)(3) and other homogeneous catalysts modified with bases (amines and fluoride ion). Pyridine additive was partly hydrogenated and then alkylated to N-alkylpiperidines. Nucleophilic attack of fluoride ion on the substrate as well as difluorocarbene formation and hydrogenolysis in the coordination sphere of rhodium are the possible crucial steps leading to the gaseous products. (c) 2008 Elsevier B.V. All rights reserved.