This article reports a novel method for preparing supported NiW hydrodesulfurization (HDS) catalysts with tunable size and morphology of active phases to achieve highly selective HDS performance in hydro-upgrading fluid catalytic cracking (FCC) naphtha. The proposed approach features the combined use of W-based hybrid nanocrystals (HNCs) as the W precursor and the promoting effect optimization of Ni promoter. The W-based HNCs synthesized under mild hydrothermal conditions are monodispersed particles with an average size of ca. 2 nm and show a core-shell structure with W6O192- as the inorganic core and short-chain quaternary ammonium cations as the organic shell. The use of W-based HNCs facilitates the formation of highly dispersed W species and WS2 active phases with enhanced stacking, thus yielding a larger number of accessible Ni-W-S edge sites upon nickel impregnation. Moreover, we found that the advantageous W dispersion in the HNC-derived monometallic catalyst precursor allows further modification of the size and morphology of the active phase via the optimized incorporation of Ni promoter, leading to the formation of Ni-W-S edge sites with a lower percentage of brim sites and thereby resulting in considerably higher selective HDS performance for FCC naphtha than its counterpart prepared by the conventional impregnation method. The proposed approach makes it easy to tune the size and morphology of WS2 nanoparticles, shedding light on the rational design of supported WS2 catalysts for FCC naphtha selective HDS. (C) 2015 Elsevier Inc. All rights reserved.