To delve into the law of hydrocarbon production in microwave-assisted catalytic fast pyrolysis (MACFP) of corn straw, physical mixed Mesoporous Crystalline Material-41 (MCM-41) and Zeolite Socony Mobile-5 (ZSM-5) catalyst prototypes were exploited in this study. Besides, the effects exerted by temperature of reaction and MCM-41/ZSM-5 mass ratio were explored. As revealed from the results, carbon outputs of hydrocarbons rose initially as the temperature of MACFP rose and reached the maximal data at 550 °C; subsequently, it declined as reaction temperature rose. Moreover, the MCM-41/ZSM-5 mass ratio of 1:2 was second-to-none for hydrocarbon formation in the course of biomass MACFP. It was reported that adding MCM-41 can hinder coke formation on ZSM-5. Furthermore, MCM-41/ZSM-5 mixture exhibited more significant catalytic activity than ZSM-5/MCM-41 composite, demonstrating that hydrocarbon producing process can be stimulated by a simple physical MCM-41 and ZSM-5 catalysts mixture instead of synthesizing complex hierarchically-structured ZSM-5/MCM-41 composite.