Channels in microfluidic glass chips manufactured with the alternative powder blasting technology were permanently coated with poly(vinyl alcohol) (PVA) in order to improve the performance in microchip electrophoresis. The performance of coated and uncoated powder-blasted (pb) devices as well as coated and uncoated wet chemical etched (wc) chips was compared in electrophoretic separations of fluorescently labeled test compounds. The limited electrophoretic resolution obtained in pb-chips could significantly be improved by coating the channels with PVA. The resolution of test compounds in such coated pb-devices was even higher than in uncoated wc-chips. PVA-coated pb-chips could also successfully be applied in chiral separations. While in an uncoated pb-chip using a cyclodextrins buffer only one broad signal was obtained, two well-resolved signals were obtained in a coated device.