Understanding the structure-reactivity relationship at the atomic scale is of great theoretical importance for rational design of highly active catalysts, which has long been a central concern in catalysis communities and interface science. Herein, we developed a high-efficiency catalyst for catalytic oxidation of C6H12 by poststructural decoration on well-defined single-crystal facets of hematite. Especially for Cl-decorated {012} facets, the conversion and KA oil selectivity are improved about 3.4 times and 2 times, respectively. A better catalytic performance of the newly formed active site is derived from the charge difference between Cl and the neighboring outmost O atoms, which is affected by the geometric and electronic structures of the original catalyst surface. Based on the experimental results and the theoretical analysis, we concluded that the contribution of various O terminations to Cl-decoration follows the order O(I) > O(III) > O(II). Cl-decorated {001} facets show the highest intrinsic activity, whereas Cl-decorated {012} facets show the best catalytic performance because of their more active sites for Cl-decoration.