Miniaturization of chemical analysis using microfabrication is an emerging technology. The use of polymeric materials as opposed to conventional glass substrate is also a promising alternative. As most polymeric materials are hydrophobic relative to glass, we describe here the implication for the loading process of electroosmotic flow (EOF) when a three-phase (solid-liquid-vapor) contact line exists. The presence of these interfaces can result in a large Laplace pressure that resists EOF and hence hinders its flow performance. This effect depends on the phenomenological contact angle at the solid-liquid interface. In our model for EOF, we considered simultaneously the presence of an electric double layer, liquid slips via a weaker solid-liquid interaction and Laplace pressure across a liquid-vapor interface. (C) 2004 American Institute of Physics.