Elevated pressure secures the highest fixed-carbon yields of charcoal from corncob. Operating at a pressure of 0.8 MPa, a flash-carbonization reactor realizes fixed-carbon yields that range from 70 to 85% of the theoretical thermochemical equilibrium value from Waimanalo corncob. The fixed-carbon yield is reduced to a range from 68 to 75% of the theoretical value when whole Waimanalo corncobs are carbonized under nitrogen at atmospheric pressure in an electrically heated muffle furnace. The lowest fixed-carbon yields are obtained by the standard proximate analysis procedure for biomass feedstocks; this yield falls in a range from 49 to 54% of the theoretical value. A round-robin study of corncob charcoal and fixed-carbon yields involving three different thermogravimetric analyzers (TGAs) revealed the impact of vapor-phase reactions on the formation of charcoal. Deep crucibles that limit the egress of volatiles from the pyrolyzing solid greatly enhance charcoal and fixed-carbon yields. Likewise, capped crucibles with pinholes increase the charcoal and fixed-carbon yields compared to values obtained from open crucibles. Large corncob particles offer much higher yields than small particles. These findings show that secondary reactions involving vapor-phase species (or nascent vapor-phase species) are at least as influential as primary reactions in the formation of charcoal. Our results offer considerable guidance to industry for its development of efficient biomass carbonization technologies. Size reduction handling of biomass (e.g., tub grinders and chippers), which can be a necessity in the field, significantly reduces the fixed-carbon yield of charcoal. Fluidized-bed and transport reactors, which require small particles and minimize the interaction of pyrolytic volatiles with solid charcoal, cannot realize high yields of charcoal from biomass. When a high yield of corncob charcoal is desired, whole corncobs should be carbonized at elevated pressure. Under these circumstances, carbonization is both efficient and quick