Preparation of molybdenum phosphide with cluster size is important for enhancing its catalytic activity. Herein, ZSM-5 microspheres consisting of nanocrystals (ZSM-S-NA) were synthesized and used for the preparation of supported MoP catalysts (MoP/ZSM-5-NA). ZSM-5-NA exposes a large outer surface with abundant acidic sites, which benefit the strengthening metal-support interaction and have interconnected macronanoporous structure promoting the metal active component diffusion into the interior. Most of the MoP-active phases with cluster size (<1 nm) were highly dispersed on the surface of the MoP/ZSM-S-NA catalyst, whereas large MoP particles (5-10 nm) were formed on the SiO2 support because of the weak metal-support interaction. The intrinsic activity of MoP/ZSM-5-NA (r(obs) = 3.4 X 10(-4) mol-kg(-1).s(-1)) was higher than that of the SiO2-supported MoP catalyst (2.3 X 10(-4) mol.kg(-1)s(-1)) in the phenanthrene hydrogenation. Additionally, the calcined MoP/ZSM-5-NA sample was presulfided, followed by reduction, and the sulfur species incorporation into MoP phases led to the catalyst presenting high activity (4.1 X 10(-4) mol-kg(-1)-s(-1)).