Novel carbon molecular sieve (CMS) compositions comprising carbonized vinylidene chloride copolymer having micropores with an average micropore size ranging from 3.0 to 5.0. These materials offer capability in separations of gas mixtures including, for example, propane/propylene; nitrogen/methane; and ethane/ethylene. Such may be prepared by a process wherein vinylidene chloride copolymer beads, melt extruded film or fiber are pretreated to form a precursor that is finally carbonized at high temperature. Preselection or knowledge of precursor crystallinity and attained maximum pyrolysis temperature enables preselection or knowledge of a average micropore size, according to the equation ?=6.09+(0.0275×C)−(0.00233×T), wherein ? is the average micropore size in Angstroms, C is the crystallinity percentage and T is the attained maximum pyrolysis temperature in degrees Celsius, provided that crystallinity percentage ranges from 25 to 75 and temperature in degrees Celsius ranges from 800 to 1700. The beads, fibers or film may be ground, post-pyrolysis, and combined with a non-coating binder to form extruded pellets, or alternatively the fibers may be woven, either before or after pre-treatment, to form a woven fiber sheet which is thereafter pyrolyzed to form a woven fiber adsorbent.