Mica substrates were activated by a plasma method leading to OH-functionalized surfaces to which an atom transfer radical polymerization (ATRP) radical initiator was covalently bound using standard siloxalle protocols. The unprecedented covalently immobilized initiator underwent radical polymerization with tert-butyl acrylate, yielding for the first time end-grafted polymer brushes that are covalently linked to mica. The initiator grafting oil the mica substrate was confirmed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), while the change in the water contact angle of the OH-activated mica Surface was used to follow the change in Surface coverage of the initiator oil the surface. The polymer brush and initiator film thicknesses relative to the virgin mica were confirmed by atomic force microscopy (AFM). This was done by comparing the atomic step-height difference between a protected area of freshly cleaved mica and a zone exposed to plasma activation, initiator immobilization, and then ATRP.