Laser pyrolysis (LP) using a CO2 laser was used to rapidly heat Avicel cellulose char with and without doping by Na, K, Ca, Mg, Co, Ni, Cu, Pd, and Zn as their respective acetates in the uncharred cellulose. LP-molecular beam mass spectrometry (LP-MBMS) was used to probe the chemistry of the pyrolysis of the chars and to characterize the initial volatilized reacting plume of pyrolyzate. The mass spectra were deconvoluted by multivariant factor analysis (MVA). MVA revealed that, at the 1 wt% doping level, Cu did little to change the pyrolysis chemistry of cellulose char, among the other metals, Na, K, Ca, Mg, Co, Ni, and Zn did effect the pyrolysis chemistry, and Co and to a lesser extent Pd acted by a differing mechanism. A liquid N-2 cold trap coated with diphenyldisulfide was used to understand the chemistry of the evolving pyrolyzate plume. The washings from this trap were analyzed by gas chromatography-mass spectrometry (GC-MS) allowing for speciation of both the chemically trapped radicals and the nonradical volatiles. It was clear that the species trapped had a much greater degree of methyl substitution than observed in the LP-MBMS. Radicals trapped included hydrogen, methyl, and phenyl but did not include cyclopentadienyl or benzyl. Zn, which was volatilzed by the LP, had the highest yield of radicals. In general, the cold-trapped 1 and 2 aromatics had a higher level of methyl substitution. Cu and Pd increase the formation of aromatic species during the pyrolysis of cellulose char and have a variable effect on radical production. Na, K, Mg, Ca, Co, and Ni suppress the formation of aromatic species and have a variable effect on radical production.