A capillary microchannel (CM) containing TiO(2)-coated ZnO nanorod arrays was applied as a novel microfluidic device to selectively bind and enrich phosphopeptides. The device was prepared by pumping a TiO(2) sol into a CM containing preformed ZnO nanorod arrays. Different thicknesses of the TiO(2) coating were obtained by controlling the flow duration of TiO(2) sol. The modified CM achieved uninterrupted high-throughput introduction, capture and enrichment of phosphopeptides using continuous-flow operation. The microfluidic device based on the modified CM showed great selectivity, sensitivity and durability for the enrichment of phosphopeptides from tryptic protein digests. These results suggest that microfluidic chips employing this strategy can be used for rapid and high-throughput enrichment of phosphopeptides from complex mixtures.