Sol–gel process is a very unique wet chemical method for producing advanced materials in various areas of research. An increasingly evolution trend of this process is to combine with other technologies, such as surface modification, hybridization, templating induction, self-assembly, and phase separation, for preparing new materials possessing controllable shape, unique microstructure, superior properties, and special application. The review aims to present the synthesis of several typical sol–gel-derived materials (monodisperse nanoparticles, hybrid coatings, hollow microspheres, aerogels, and porous monoliths) via sol–gel process combining with other technologies . Some examples of application of the sol–gel-derived materials are also included.