In response to the "Crude-to-Chemicals" trend in the refining industry and the growing demand for light olefins and aromatics, high-temperature fast catalytic pyrolysis offers an efficient route for converting petroleum hydrocarbons into value-added chemicals. This study investigates the pyrolysis of 1-alkenes, n-alkanes and n-alkylbenzenes with varying carbon numbers as model petroleum hydrocarbons by Pyrolysis-Gas Chromatography-Mass Spectrometry/Flame Ionization Detector (Py-GC-MS/FID). The experiments are conducted under fast pyrolysis conditions, reaching a final temperature of 700℃ at a heating rate of 20℃/ms. The modulation of product selectivity by acidic ZSM-5, acidic USY, and basic CaAl catalysts is systematically examined, with thermal pyrolysis serving as a baseline. The results demonstrate that the selectivity for C2-C4 light hydrocarbons follows the order: ZSM-5 acidic catalyst>CaAl basic catalyst>thermal pyrolysis>USY acidic catalyst, whereas the selectivity for BTX (benzene, toluene, and xylenes) is ordered as: acidic catalysts (ZSM-5 and USY)>CaAl basic catalyst>thermal pyrolysis. Specifically, for 1-alkenes over ZSM-5, the C2-C4 light hydrocarbons selectivity ranges from 31% to 51%, decreasing with increasing carbon number. For n-alkanes, the C2-C4 light hydrocarbons selectivities are 43%~68% over ZSM-5 and 30%~61% over USY. For n-alkylbenzenes over ZSM-5, this selectivity reaches 34%~62%. These trends are attributed to the synergistic effect of ZSM-5's acidic sites and shape-selective channels, which suppress bimolecular side reactions, including hydrogen transfer and oligomerization, and favor monomolecular β-scission into smaller molecules. In contrast, the strong acidity and hierarchical pore structure of USY promote hydrogen transfer and secondary reactions, leading to a higher yield of C5+ alkanes. The CaAl catalyst operates primarily via a radical-chain mechanism, suppressing hydrogen transfer and enhancing olefin selectivity, albeit with limited overall cracking severity. These findings elucidate the intrinsic relationship between hydrocarbon structure, catalyst properties, and product selectivity, providing theoretical and practical insights for the development of high-temperature fast catalytic pyrolysis technologies.