For the initial activation of short-chain alkanes over Zn/HZSM-5 catalyst, the impact of branching degree and carbon numbers of reactants on the competition between dehydrogenation and cracking was systematically studied by experiment and calculation. The experiments were carried out on fixed-bed flow micro-reactor over HZSM-5 and Zn/HZSM-5 catalysts, by using n-butane/i-butane and propane/n-hexane as reactants with different branching degree and carbon numbers. Compared with HZSM-5, Zn/HZSM-5 obviously accelerated the cracking of C-H bond of short-chain alkanes and increased the selectivity of BTX aromatics. The selectivity to hydrogen produced from n-butane and n-hexane was higher than i-butane and propane, respectively. On the contrary, the selectivity to methane was correspondingly lower, i-butane and propane with high percentage of terminal carbons effectively suppressed the dehydrogenation. The key point to decide the reaction process through dehydrogenation or cracking is the initially activated sites of reactant. To verify this conclusion, theoretical calculations were carried out. The results showed that the (Zn-O-Zn)(2+) Lewis acid sites of Zn/HZSM-5 accelerated the cracking of C-H and C-C bond simultaneously. Namely, if the initial activation occurred on the terminal carbons of reactant, the subsequent reaction would be kinetically competitive between cracking and dehydrogenation. Cracking would inevitably occur (thermodynamically favorable), and then the by-products of methane and ethane were produced in large amount. If the initial activation occurred on the internal carbons, the dehydrogenation reaction is kinetically favorable, which is beneficial to reducing the dry gas production. Therefore, cracking is more favorable than dehydrogenation for smaller alkanes and branched alkanes with high percentage of terminal carbons. The percentage of terminal carbons of short-chain alkanes determines the probability of dehydrogenation route over Zn/HZSM-5. The activation of the internal carbon via the dehydrogenation route is more favorable for the normal alkane with higher carbon number during the first stage of conversion suppressing the formation of the by-products of methane and ethane. [GRAPHICS] .