Carbon molecular sieves, useful in the separation of air into oxygen and nitrogen, are improved through modification of the micropores of the sieve by contact with the pyrolysis products of a carbon-containing compound in the gaseous state diluted with helium, with or without nitrogen as a part of the diluting gas. Volatile organic compounds, such as trimethylcyclohexane, are used with the diluent gas to narrow the micropore openings of a carbon molecular sieve and increase its kinetic selectivity for oxygen adsorption. Carbon dioxide and helium or argon in the diluent gas are used to open pores available to contacting gases.