T he development of highly selective and sensitive analytical techniques has been a driving force for unprecedented advances in biotechnology, gene engineering, and drug discovery. Capillary electrophoresis (CE) is becoming a wider accepted analytical method in biology and medicine. CE offers short analysis time, high resolution, and minute consumption of samples and reagents, making it an attractive technique for mass bioassays and drug screening. Since the last Analytical Chemistry review in this field, 1 there have been published over 10 000 articles with CE as a topic. Within a variety of studies concerning CE, we have identified the intensively developing area of reversible biomolecular interactions which are defined as highly selective noncovalent binding of ligands with biomolecules. These affinity interactions control cell recognition, signal transduction, immune response, DNA replication, gene expression, and other cellular processes. The knowledge of quantitative parameters of binding reactions (equilibrium and/ or rate constants) is essential for understanding the mechanisms of biological processes, which these reactions regulate. The present review covers a 3-year period between January 2012 and November 2014. We have attempted to select studies that demonstrate the newest and most impactive developments in the field of biomolecular affinity interactions.