Alkylation of benzene with n-hexane was performed over H-ZSM-5 and monometallic Ga- and Pt- and bimetallic Ga- and Pt-modified ZSM-5. The influence of the particle size and the method of incorporation of Ga (during hydrothermal synthesis, by solid-state ion exchange, or by liquid-state ion exchange) was determined. The presence of Pt and well-dispersed extraframework Ga in H-ZSM-5 increased the selectivity in alkylation and suppressed cracking reactions. Well-dispersed Pt particles led to better catalytic performance. The method of Ga incorporation played an important role in obtaining higher selectivity to alkylation products and in the suppression of side reactions. Up to 93% selectivity in alkylation (of which > 95% was to 2-phenylhexane) was reached over 2 wt% Pt/H-Ga(f)ZSM5, in which Ga occupied framework positions. We propose that the close proximity of very small Pt nanoparticles and Ga-(OH)-Si acid sites results in the optimal bifunctional catalyst for selective production of 2-phenylhexane from benzene and n-hexane. During the reaction, the catalyst deactivated, most probably due to the sintering of the Pt particles.