The self-assembly of small surfactants and Pluronic® amphiphilic copolymers has enabled the synthesis of a range of ordered mesoporous materials with high surface area, diverse compositions, variable pore structures and tunable pore sizes. It has recently been realized that non-Pluronic block copolymers can be used as robust templates for the synthesis of novel and high-performance mesoporous materials with crystalline frameworks, ultra-large pores, and abundant pore symmetries, which are not accessible using the Pluronic counterparts. In this review, we introduce the principle of self-assembly of block copolymers and their phase separations, and summarize recently developed synthetic methods and strategies for ordered mesoporous silicas, metal oxides, carbons and metals which have shown superior performances for applications in various fields, including solar cells, batteries, fuel cells, and sensors.