We report the coating of poly(dimethylsiloxane) (PDMS) microchannels using transition metal sol-gel chemistry and the subsequent characterization of the coatings. The channels were created using soft polymer lithography, and three metal alkoxide sol-gel precursors were investigated, titanium isopropoxide, zirconium isopropoxide, and vanadium triisobutoxide oxide. The metal alkoxides were diffused into the sidewalls of a PDMS channel and subsequently hydrolyzed using water vapor. This procedure resulted in the formation of durable metal oxide surfaces of titania, zirconia, or vanadia. The resulting surfaces were characterized using contact angle, X-ray photoelectron spectroscopy (XPS), Raman, transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and electroosmotic mobility (EOM) measurements. All of the metal oxide-modified PDMS surfaces were significantly more hydrophilic than native PDMS. Contact angles for the coatings were 90 for PDMS-ZrO2, 61 degrees for PDMS-TiO2, and 19 for PDMS-vanadia. XPS showed the presence of titania, zirconia, and vanadia on the PDMS surface. XPS spectra also showed no chemical modification of the PDMS after the in situ deposition of the particles either in the Si-O, Si-C, or C-H bonds of the PDMS. The particles deposited in situ were imaged with TEM and were found to be homogeneously distributed throughout the bulk of the PDMS. EOM measurements of the inorganic coatings were stable over a period of at least 95 days. Both cathodic and anodic EOMs could be generated depending upon buffer pH used. The points of net zero charge for PDMS-TiO2, PDMS-ZrO2, and PDMS-vanadia channels were calculated using EOM versus pH measurements and were found to be 4.1 +/- 0.25, 6.1 +/-0.2, and 7.0 +/- 0.43; respectively. In addition to modifying PDMS channels with inorganic coatings, these inorganic coatings were derivatized with various organic functionalities including oligoethylene oxide (OEO), amino, perfluoro, or mercapto groups using silane chemistry. Contact angle measurements for perfluoro, mercapto, amino, and OEO-coated surfaces yielded contact angles of 120, 76, 45, and 23, respectively. These contact angles did not change over the period of 95 days. OEO-coated channels reduced the EOM by 50% from native PDMS-TiO2 to 0.9 +/- 0.05 x 10(-4) cm(2)/V.s (n = 5, 5.5% RSD).