Controlling and manipulating liquids and analytes at the sub-millimeter scale is a challenge that frequently requires new methods to be developed. Indeed, scaling-down of traditional macroscopic ideas often fails. For instance, pumping liquids using pressure differences is often impractical and counterproductive because the resulting parabolic flow profile deforms sample zones. As the size of the system shrinks, the surface-to-volume ratio increases and interfacial effects become dominant. This actually opens new possibilities since the phenomenon of electroosmotic flow (EOF), wherein a fluid is made to move relative to a stationary charged boundary, can then be exploited to design efficient microfluidic devices. In this chapter, we review the fundamental principles of EOF as well as some of the methods used to coat channel walls and reduce the impact of EOF in situations where it would be unfavorable for the device performance.