A polyvinylidene fluoride (PVDF) pyrolyzate adsorbent is described, having utility for storing gases in an adsorbed state, and from which adsorbed gas may be desorbed to supply same for use. The PVDF pyrolyzate adsorbent can be of monolithic unitary form, or in a bead, powder, film, particulate or other finely divided form. The adsorbent is particularly suited for storage and supply of fluorine-containing gases, such as fluorine gas, nitrogen trifluoride, carbo-fluoride gases, and the like. The adsorbent may be utilized in a gas storage and dispensing system, in which the adsorbent is contained in a supply vessel, from which sorbate gas can be selectively dispensed.