In capillary electrophoresis (CE), analytes are separated along the axis of a single microcapillary by virtue of their differential migration in an applied electric field. CE can also be performed in channels etched on solid substrates such as glass or PDMS and can be integrated into a microfluidic chip with a complex network of electric and fluidic circuits. The measure of quality of a CE instrument is resolution which is limited fundamentally by mixing due to various physical processes. The theoretical limit on the best separation that can be achieved is set by molecular diffusion, which is inevitable. The goal is to eliminate or minimize the other sources of dispersion by design. This chapter provides an overview of the various mechanisms of band broadening and the mathematical results that make it possible to estimate their relative contributions.