The binary cooperative complementary phenomenon refers to two opposite but cooperative and complementary species or states, which can be observed from atom scale to universe. When binary cooperative complementary pairs in nanoscale are separated by a related characteristic physical distance, the electron and energy transfer through interface can be well tuned, consequently the macroscopic property of a nanomaterial can be highly enhanced, such materials are defined as binary cooperative complementary interfacial nanomaterials (BCCINMs). A variety of BCCINMs have been developed and exhibited outstanding performance. In this review, for fabrication, various binary cooperative complementary pairs are summarized, the obtained BCCINMs and building blocks are classified into OD, 1D, 2D and 3D materials, some effective methods and advices are also given. In the following, various properties and applications of existing BCCINMs are introduced. In the next part, BCCINMs are extended, multiple binary cooperative complementary pairs and smart BCCINMs are introduced. Moreover, temporal and spatial regulation is also essential for BCCINMs such as bulk heterojunctions and core-shell quantum dots. There is plenty of room at the bottom for BCCINMs, in the future, more binary cooperative complementary pairs should be employed, effective methods should be created and applied to assemble binary cooperative complementary pairs with suitable distribution size and for spatial and temporal regulation. (C) 2018 Elsevier Ltd. All rights reserved.