Zeolite socony mobil-5 (ZSM-5) is a common catalyst used for biomass pyrolysis. Nevertheless, the quantitative information on the catalytic behavior of ZSM-5 on biomass pyrolysis is absent so far. This study focuses on the catalytic pyrolysis phenomena and mechanisms of biomass wastes using ZSM-5 via thermogravimetric analyzer and pyrolysis-gas chromatography/mass spectrometry, with particular emphasis on catalytic level identification and aromatic hydrocarbons (AHs) formation. Two biomass wastes of sawdust and sorghum distillery residue (SDR) are investigated, while four biomass-to-catalyst ratios are considered. The analysis suggests that biomass waste pyrolysis processes can be divided into three zones, proceeding from a heat-transfer dominant zone (zone 1) to catalysis dominant zones (zones 2 and 3). The indicators of the intensity of difference (IOD), catalytic effective area, catalytic index (CI), and aromatic enhancement index are conducted to measure the catalytic effect of ZSM-5 on biomass waste pyrolysis and AHs formation. The maximum IOD occurs in zone 2, showing the highest intensity of the catalytic effect. The CI values of the two biomass wastes increase with increasing the biomass-to-catalyst ratio. However, there exists a threshold for sawdust pyrolysis, indicating a limit for the catalytic effect on sawdust. The higher the catalyst addition, the higher the AHs proportion in the vapor stream. When the biomass-to-catalyst ratio is 1/10, AHs formation is intensified significantly, especially for sawdust. Overall, the indexes conducted in the present study can provide useful measures to identify the catalytic pyrolysis dynamics and levels.