Dry reforming of methane has been systematically investigated over a series of x‐Co@SiO2‐y catalysts where x is the Co particle size ranging from 11.1 to 121.3 nm while y denotes the silica shell thickness ranging from 6.0 to 21.9 nm. Various techniques including TEM, XRD, H2‐TPR/‐TPD, XPS, BET, O2‐TPO, TG, and H2‐TPSR‐MS were employed to characterize physicochemical properties of catalysts. H2‐TPR and XPS results indicate that the core–shell interaction is dependent on the core size: the smaller the Co particle size is; the stronger the core–shell interaction. The investigations employing H2‐TRSR‐MS and XPS on the spent catalysts demonstrated that a fraction of metallic Co was re‐oxidized on a large‐core catalyst such as 121.3‐Co@SiO2‐72.2 during the reaction, and such oxidation leads to lower catalytic activity and stability. O2‐TPO results indicated that the catalyst with smaller core size caused significant coking. TG analysis together with TEM investigation on the used samples suggested that carbon deposition is notably core‐size‐dependent and responsible for deactivation of the small‐core catalyst. Among various core–shell structured catalysts, 27.8‐Co@SiO2‐14.3 showed superior activity and durability, owing to the well‐balanced property between coking and anti‐oxidation of Co cores.