Au superatoms composed of a specific number of gold atoms (denoted as Au) are particularly well-defined catalysts, permitting to precisely correlate their catalytic behavior with their unique structure and electronic properties and achieve the controllable obtainment of the desired products in uncertain catalytic processes. Au superatoms with electron-deficient shell and electron-rich core are utilized to catalyze the partial oxidation of styrene with tert-butyl hydroperoxide as the oxidant. The partial oxidation of styrene typically produces benzaldehyde and epoxide as major products. Herein, we report a strategy for controlling the catalytic selectivity by exploring the promotion effect of acetonitrile. High selectivity for benzaldehyde (similar to 100%) under one set of conditions and for epoxide (>95%) under the other set of conditions has been respectively attained by tuning the site-specific catalytic properties of Au,, superatoms with specific core shell structure. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.