The synthesis of ZSM-5 microparticles (MPs) possesses scientific and industrial importance due to the corresponding kinetic effects and operation issues. In this paper, a simple and scalable crystal seed growth approach was developed to synthesize ZSM-5 MPs, without an organic template, for the catalytic hydration of cyclohexene to cyclohexanol. As ZSM-5 sub-microparticles (SMPs) were used as the crystal seeds, the as-synthesized ZSM-5 MPs exhibit higher crystalline degrees and larger sizes, with an average diameter up to 8.78 μm, than that of commercial ZSM-5 SMPs. The as-synthesized ZSM-5 MPs possess typical micrometer diameters. As catalysts in the hydration of cyclohexene to cyclohexanol, the ZSM-5 MPs exhibit high catalytic performances, in a long running experiment of up to 1000 h, and a superior sedimentation property compared to commercial ZSM-5 SMPs.