It has been shown that sodium stannate with superbasic sites generated on its surface can be obtained through simple thermal treatment of sodium stannate hydrate in pure N(2). In this study, we analyzed the as-prepared materials using powder X-ray diffraction, X-ray photoelectron spectroscopy, and N(2) physisorption methods. The superbasic sites were characterized by techniques of Hammett indicators and temperature-programmed desorption using CO(2) as adsorbate. It was shown that after undergoing calcination at 623 K, there are ample superbasic sites on sodium stannate: up to 0.254 mmol/g. The super-basicity of the materials was further confirmed by employing the 1-hexene as well as cyclohexa-1,4-diene double bond isomerization reactions. The superbasicity is attributed to the higher electron-donating ability of surface O(2-). The sodium stannate samples showed excellent catalytic efficiency towards selected reactions, namely the dehydrogenation of propa-2-nol, Michael addition of electron-deficient olefins, and transesterification of cyclic carbonate with methanol. It was observed that with rise of heat-treatment temperature from 573 to 623 K. both superbasicity and catalytic activity increased, reaching a maximum at 623 K, and then declined. It is deduced that catalytic efficiency is closely related to superbasicity of the sodium stannate catalysts. (C) 2011 Elsevier B.V. All rights reserved.