High-efficiency utilization of CO₂ facilitates the reduction of CO₂ concentration in the global atmosphere and hence the alleviation of the greenhouse effect. The catalytic hydrogenation of CO₂ to produce value-added chemicals exhibits attractive prospects by potentially building energy recycling loops. Particularly, methanol is one of the practically important objective products, and the catalytic hydrogenation of CO₂ to synthesize methanol has been extensively studied. In this review, we focus on some basic concepts on CO₂ activation, the recent research advances in the catalytic hydrogenation of CO₂ to methanol, the development of high-performance catalysts, and microscopic insight into the reaction mechanisms. Finally, some thinking on the present research and possible future trend is presented.