We have previously demonstrated the successful application of multivariate statistical(i.e. chemometric) techniques to the classification of casework fire debris based on gasoline content, with the objective to expedite the data interpretation process for the forensic analysis of fire debris. We have also shown thatit is possible to classify simulated fire debris based on gasoline content using simulated fire debris; however, models trained on simulated debris are not applicable to casework samples without a significant loss in model accuracy.Apreviously developed simulation protocolthat works wellfor generating debris to train human analysts was inadequate for training either partial least-squares discriminant analysis (PLS-DA) or soft independent modelling by class analogy (SIMCA) models to identify casework debris due mainly to its inability to generate a sufficient amount of benzene, toluene, ethylbenzene, and xylenes (BTEX) and non-aromatic hydrocarbon compounds. This method relied on pyrolyzing materials at 400 ◦C. Here we examine the effects of pyrolysis conditions on household materials, including spruce plywood, vinyl sheet flooring, polyethylene terephthalate (PET) carpet, Nylon 6 carpet, polyurethane (PU) foam carpet underlay, asphalt shingle, medium-density fireboard (MDF) shelving, and spruce timber at temperatures above 400 ◦C, in an attempt to generate additional BTEX and non-aromatic hydrocarbon compounds for the realistic simulation of fire debris. The work presented here showed that C3- to C5-alkylbenzenes, which are abundant in gasoline, were generally absent from the pyrolysates of all materials studied and at all temperatures studied (400, 700 and 900 ◦C), only appearing in trace amounts on rare occasions. Based on our results, we propose that accurate simulation of fire debris could be achieved with a mixture of carpets, carpet underlay, and vinyl flooring pyrolyzed at 700 ◦C; spruce plywood pyrolyzed at 900 ◦C, and asphalt shingles pyrolyzed at 400 and 700 ◦C. These conditions generated a substantial amount of BTEX and non-aromatic hydrocarbons in the debris matrix background. The testing of this “recipe” for generating simulated debris for training chemometric models that can classify casework debris is left for future experimentation.