Surface structure plays a vital role in the functionalization of polymer. In the past decades, various functional surfaces with diversified microstructures have been fabricated through electrospinning, lithography, plasma processing to achieve wide applications in optics, electronics, biology, chemistry and so on. However, there is still a huge demand to develop new strategies for regulating polymer’s surface microstructure to meet the growing requirements of economic and technological development. This review gives a brief instruction of current research on controlling surface structure from the perspectives of molecule diffusion, internal stress, external stress, and the cooperation of these different factors. Besides, the future development in controlling surface microstructure of polymer materials has been discussed.