The prosperity of Silicon Valley is built upon a foundation of wood charcoal that is the preferred reductant for the manufacture of pure silicon from quartz. Because ordinary pyrolysis processes offer low yields of charcoal from wood, the production of silicon makes heavy demands on the forest resource. The goal of this paper is to identify process conditions that improve the yield of charcoal from wood. To realize this goal, we first calculate the theoretical fixed-carbon yield of charcoal by use of the elemental composition of the wood feedstock. Next, we examine the influence of particle size, sample size, and pressure on experimental values of the fixed-carbon yields of the charcoal products and compare these values with the calculated theoretical limiting values. The carbonization by thermogravimetric analysis of small samples of small particles of wood in open crucibles delivers the lowest fixed-carbon yields, closely followed by standard proximate analysis procedures that employ a closed crucible and realize somewhat improved yields. The fixed-carbon yields (as determined by thermogravimetry) improve as the sample size increases and as the particle size increases. Further gains are realized when pyrolysis occurs in a closed crucible that hinders the egress of volatiles. At atmospheric pressure, high fixed-carbon yields are obtained from 30 mm wood cubes heated in a closed retort under nitrogen within a muffle furnace. The highest fixed-carbon yields are realized at elevated pressure by the flash carbonization process. Even at elevated pressure, gains are realized when large particles are carbonized. These findings reveal the key role that secondary reactions, involving the interaction of vapor phase pyrolysis species with the solid substrate, play in the formation of charcoal. Models of biomass pyrolysis, which do not account for the impacts of sample size, particle size, and pressure on the interactions of volatiles with the solid substrate, cannot predict the yield of charcoal from biomass. These findings also offer important practical guidance to industry. Size reduction of wood feedstocks is not only energy and capital intensive; size reduction also reduces the yield of charcoal and exacerbates demands made on the forest resource.