Polymer microarrays are a powerful sample format for high-throughput materials discovery. We describe a polymer microarray prepared via ink-jet printing for the purpose of screening novel biomaterials. Ink-jet printing has advantages over other printing techniques including avoiding contact with the surface, preventing damage to fragile substrates, and the control of the drop volume to control the amount of material deposited. We investigate a method for ink-jet printing a library of monomer solutions, which are subsequently polymerized in-situ to form the polymer microarray. Imaging of the polymer microarray using time-of-flight secondary ion mass spectrometry is employed to map specific ions characteristic of the constituent monomers and identify which chemical functionalities are present at the surface of each polymer. This is particularly important in determining the quality of the array and understanding the interactions that occur at the interface between a material and a biological organism. Copyright © 2012 John Wiley & Sons, Ltd.