A detailed investigation was carried out to develop novel pore- and morphology-controllable ETS-10 zeolite. The XRD, N-2 adsorption/desorption, SEM, TEM and Si-29 NMR MAS results proved that a series of hierarchical ETS-10 zeolites was successfully synthesized and more importantly, their morphologies and pore sizes can be freely confined in the desired range under the mesoporogen, morphology- and structure-directing actions of different additives. What's more, the close relationship between various additives and raw materials especially titanium source was discussed, which played an active part in morphology change and hierarchical pores formation. This can be ascribed to the special reducibility of inorganic Ti source, system liquidity and pH, and the enhanced inorganic species dissolution. Finally, the synthesized hierarchical ETS-10 materials were used as heterogeneous catalysts for different biomass-derivatives hydrogenation. Remarkably catalytic performance can be attributed to the unique TiO6 octahedra carrying two negative charges that strengthens the interaction with active metal species, and thus improves their dispersion. Moreover, the inherent strong Lewis basicity and moderate Lewis acidity favor the oriented conversion of reactants. The controllably hierarchical structure and morphology benefit exposure of more highly dispersed active sites and prolong the catalyst life circle. Especially, an analogous molecular-recognition pattern was found by using sodium lignosulphonate, which is identified as the leading role in noticeably enhancing the catalytic activity and selectivity of the correspondingly ETS-10-based catalyst.