Reactive polymer coatings that undergo regioselective reactions with target biomolecules are provided. The polymers of the coatings are deposited via chemical vapor deposition and comprise one or more functional groups that exhibit regioselective bonding with a functional group or a target molecule. Such polymers include poly-xylylenes having functional groups such as alkynes or azides. The regioselective bonding of the reactive polymers provide stable immobilization of target molecules and/or ligands and can create biofunctional surfaces having a wide range of applications.