CE is gaining great popularity as a well-established separation technique for many fields such as pharmaceutical research, clinical application, environmental monitoring, and food analysis, owing to its high resolving power, rapidity, and small amount of samples and reagents required. However, the sensitivity in CE analysis is still considered as being inferior to that in HPLC analysis. Diverse enrichment methods and techniques have been increasingly developed for overcoming this issue. In this review, we summarize the recent advances in enrichment techniques containing off-line preconcentration (sample preparation) and on-line concentration (sample stacking) to enhancing sensitivity in CE for trace analysis over the last 5 years. Some relatively new cleanup and preconcentration methods involving the use of dispersive liquidliquid microextraction, supercritical fluid extraction, matrix solid-phase dispersion, etc., and the continued use and improvement of conventional SPE, have been comprehensively reviewed and proved effective preconcentration alternatives for liquid, semisolid, and solid samples. As for CE on-line stacking, we give an overview of field amplication, sweeping, pH regulation, and transient isotachophoresis, and the coupling of multiple modes. Moreover, some limitations and comparisons related to such methods/techniques are also discussed. Finally, the combined use of various enrichment techniques and some significant attempts are proposed to further promote analytical merits in CE.