Multiphase emulsions could be used as templates in considerable fields such as coating, optical materials, standard particles and biomedicine. Among various emulsion forming methods, microfluidic technology, with good monodispersity, high controllability and operation simplicity, has been widely used in the preparation of multiphase emulsions with different systems. This review would focus on the basic principles of forming multiphase emulsions, the recent progress in controlling multiphase flow in microfluidics, and preparation of functional materials with microfluidics mainly by the authors’ research group. We believe that the review will contribute to the readers in this prospective area very well. Multiphase emulsions could be used as templates in fields such as coating, optical materials, standard particles and biomedicine. Among various emulsion forming methods, microfluidic technology, with good monodispersity, high controllability and operation simplicity, has been widely used in the preparation of multiphase emulsions with different systems. This review would focus on the basic principles of forming multiphase emulsions, the recent progress in controlling multiphase flow in microfluidics, and preparation of functional materials with microfluidics mainly by the authors’ research group. to the readers in this prospective area very well.