Efficient, precise and controllable separation of target compounds in low concentration and large volume complex solutions is a world frontier in the field of chemical separation science. Solid phase extraction technology currently faces two challenges in industrial separation of low-concentration complex systems. On the one hand, it is difficult to give consideration to both of the high selective precision capture and the mild green desorption. On the other hand, solid phase extraction technology lacks efficient separation process and equipment for large scaled continuous separation. This review summarizes the research progress of new environmental responsive solid phase extraction technology, magnetic field responsive solid phase extraction technology, electric field- and ultrasound field- assisted solid phase extraction technology in order to solve the problems of current solid phase extraction technology, and achieve the efficient and precise separation for low concentration complex systems. Finally, the research and development direction of solid phase extraction technology in this application field is prospected. In this review, the key scientific issues of external field enhanced environmental responsive solid phase extraction technology, including environmental responsive problems, controllable separation problems and process amplification problems, are further discussed. Besides, measures and suggestions are proposed for the development of related fields.