Graphical Abstract A novel solid superbase with basic strength ( H_) above 26.5 was obtained through calcination of sodium stannate hydrate. It was found to show high catalytic efficiency towards the anti-Markovnikov hydroamination and hydroalkoxylation of electron-deficient olefins under mild conditions. Research Highlights ► The calcined sodium stannate was found to show superbasicity. ► The process for the generation of the superbase is of low energy consumption. ► The as-prepared material shows high catalytic efficiency under mild conditions. ► The catalyst exhibits good thermal stability and recyclability.