Development of highly active and stable catalyst for C–O bonds cracking is important in biomass conversion, in this work, we report a SiO2-encapsulated NiPt/HY core-shell catalyst for phenethoxybenzene (PEB) catalytic cracking. The as-grown silica shell with defined pores serves as a ‘storage’ to enhance local concentration of PEB and intermediate isomers and promotes catalytic cracking on NiPt/HY core. With the increase of silica shell thickness from 0 to 40 nm, PEB reaction rate has increased more than five times, and the major cracking product selectivity is raised to above 90%, which is attributed to the continuous conversion of PEB isomers within the shell. This designed structure endows the NiPt/HY@SiO2 with a high activity and no obvious deactivation in PEB cracking to corresponding phenol and aromatics. The outstanding performance benefit from the enrichment effect on the unique core-shell structure, as well as the moderate acidity originated from silica regulation. This work can be extended to the modulation of microenvironment to promote the catalytic behavior of core-shell catalysts.