This review summarizes the development and the applications of capillary electrochromatographic techniques pertinent to the analysis of proteins and peptides, which took place over the last 10 years (2006–mid‐2016). This “hybrid” technique is useful for the analysis of a broad spectrum of proteins and peptides and is an approach that is complementary to the liquid chromatographic and the capillary electrophoretic analysis. All modes of capillary electrochromatography are described here, which includes particle‐packed columns, monolithic stationary phases, and open‐tubular capillary electrochromatography.