Abstract: The present invention provides a process for the recovery of methyl chloride from a mixture thereof with isobutane. The process employs pressure swing adsorption with a size selective adsorbent having a pore opening of between about 3.7.times.3.7 Angstroms and about 4.9.times.5.7 Angstroms, such as zeolite A, clinoptilolite and mixtures thereof to selectively adsorb methyl chloride from vent streams comprising methyl chloride and isobutane and recovering a tail gas stream enriched in methyl chloride. The process may be used in applications such as treating the vent gas streams from the direct synthesis of methyl chlorosilanes. The process provides an economical route to recovering a valuable raw material in the process of making silicones and reduces the volume and methyl chloride content of the vent stream which is typically incinerated to avoid the release of halogenated hydrocarbons to the atmosphere.