Tungsten carbides exhibit excellent performance in many heterogeneous processes because of their distinctive catalytic properties. Preparation of tungsten carbides with controllable phase composition relevant to their catalytic behavior is essential yet challenging. In this study, tungsten carbides embedded in carbon spheres (WxC@CS) were fabricated through carburization of organic-inorganic hybrid precursors. W1.25C@CS with rational structure-tuning properties exhibits promising regioselectivity (reaching 91.5%) toward aryl C-O bond cleavage, specifically during hydrogenolysis of guaiacol to phenol. A structure reconstruction strategy was adopted to elucidate structure-performance relationship by transforming commercially available bulk WC from inert phase to composition-dependent active catalysts. Combined catalytic and characteristic analyses illustrate that the catalyst performance is dependent on the C-defect structure. The intimate connection between the phenol space time yield and the C/W atomic ratio on the exterior interface of the catalyst was verified. The C/W atomic ratio of 7.2 leads to the optimal catalytic performance. Density functional theory calculations were performed to define the catalytic mechanism at the atomic level. The theoretical analysis suggests an appropriate configuration of surface W and C atoms for activation of hydrogen and guaiacol molecules, rendering the intrinsic active sites for phenol production. This work provides insights into controlling the surface compositions of tungsten carbides to develop efficient C-O bond cleavage catalysts, which verifies the importance of hydrogenolysis catalysis in lignin-derived compounds involving complex O-containing guaiacols and phenolics. (C) 2018 Elsevier Inc. All rights reserved.