We have developed a novel strategy to generate self-assembled monolayer microarray (SAMs-Array) of alkanethiolates on gold surfaces for the study of human mesenchymal stem cells (hMSCs) differentiation. Electroactive alkanethiols were microarray-printed in varying densities to probe the chemical effects on stem cell differentiation. Cyclic voltammetry (CV) was used for the precise determination of the amount of alkanethiol molecules transferred and SAMs formed on the microarray. We can also control the oxidative and reductive state of each molecule displayed to cells by CV. Based on this SAMs-Array technology, we generated a platform for potential high-throughput screening of various surface chemistry effects on cell behaviors for future applications in biomaterials and tissue engineering. (C) 2011 Elsevier Inc. All rights reserved.