With the highest content of primary amine functional groups of any polymer, polyvinylamine (PVAm) is a potent tool for the modification of macroscopic and nanoparticle surfaces. Based on the free radical polymerization and subsequent hydrolysis of N-vinylformamide, PVAm is prepared as linear polymers (0.8 kDa to >1 MDa), microgels, macrogels, and copolymers. The amine groups serve as reaction sites for grafting PVAm to surfaces and for the preparation of derivatives. Coupling low-molecular-weight molecules and oligomers gives PVAm-X, where X includes hydrophobes, carbohydrate oligomers, proteins, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy), phenylboronic acids, and fluorocarbons. This contribution highlights the use of PVAm and PVAm-X to modify solid surface properties. Where possible, the PVAm properties and applications as an interfacial agent are compared to those of linear polyethylenimine, polyallylamine, and chitosan.