A computer-controlled instrument, based on scanning electrochemical microscope technology, is employed in the miniaturized combinatorial electrosynthesis of localized compound collections. Libraries of iminoquinol ethers and triazolo-pyridinium ions are generated in the wells of microtiter plates by potentiostatic electrolysis. Several experimental protocols are described and implemented. Progress of the electrolyses is monitored by microelectrode steady-state voltammetry and product formation is screened by HPLC/MS. © 2004 Elsevier Ltd. All rights reserved.