CE is considered as a powerful technique in biopharmaceutical industry, owing to its inherent advantages such as high resolution, efficient separation, and its flexibility to couple with high-sensitive detecting methods. Present review provides a summary of the applications of CE-based methods in the quality control of biopharmaceuticals according to the papers published between 1994 and July 2014. This article is divided into the sections based on different CE modes applied in the analysis of biopharmaceuticals and gives detailed information about the employed experimental conditions. At the end some overall conclusions and perspectives are given.