Crystallization experiments have been carried out in microfluidic devices to screen for polymorphs by crystallization on a range of surfaces. These devices consist of PDMS (polydimethylsiloxane) patterned with microchannels and then bonded to self-assembled monolayers (SAMs) of organic molecules on gold substrates. Barbital was crystallized in microchannels over five different SAMs functionalized with polar and nonpolar organic groups. Growth of polymorphs was examined under thermodynamic conditions from solutions at room temperature and under kinetic conditions by rapid cooling. The results of these experiments and the influence of chemically modified surfaces in microchannels in controlling polymorphism are discussed.