The 5 linear alkylbenzenes, i.e., toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, and n-pentylbenzene as fuels underwent pyrolysis at temperatures from 950 to 1450 °C in a flow reactor. Measurements of particle number size distribution, 11 monocyclic aromatic hydrocarbons, and 3 groups of polycyclic aromatic hydrocarbons (20 unsubstituted PAHs, 5 aliphatic-bridged PAHs, and 10 methyl PAHs) during the pyrolysis of linear alkylbenzenes were conducted. Results showed that the increase in side chain length suppressed the formation of particles, but ethylbenzene produced the highest particle mass and most extensive particle number size distribution. Total particle peak number concentrations exhibited a rise-then-fall trend (peaking at a critical temperature of 1050 °C) with increasing temperature regardless of the side chain length, indicating that high temperature promoted a transition from nucleation to agglomeration and coagulation. Total PAH mass concentrations were ranked in the same order with the variation of side-chain length as particle mass and peak number concentrations, indicating that soot nucleation was highly related to total PAH mass concentrations. Unsubstituted PAHs accounted for most PAHs while substituted·PAHs, including aliphatic-bridged PAHs and methyl PAHs presented 1–2 orders of magnitude less than the corresponding unsubstituted PAHs, probably distinct thermal stability and reactivity led to different growth routes between unsubstituted and substituted PAHs. Increasing the temperature from 950 to 1250 °C, the formation of high molecular weight PAHs was promoted. while a drop of high molecular weight fractions was observed above 1350 °C, which is attributed to the suppression of the formation, as well as their conversions of high molecular weight PAHs to heavier unidentified PAHs or soot. Among the test alkylbenzene fuels, the fuels with a long side chain benefit from the reduction of particles and PAHs. Furthermore, carbon atoms in aromatic rings are dominant sources of large PAHs and particles, while the carbon atoms in aliphatic side chains mainly form gas species.