Surface modified with so-called protein-repellent or antifouling polymers has become indispensable for the development of modern therapeutic and diagnostic medical devices. In this work, a series of novel well-defined poly(2-methyl-2-oxazoline)-block-poly(4-vinyl pyridine) (PMOXA-b-P4VP) diblock copolymers were synthesized by using copper-catalyzed azide-alkyne cycloaddition reaction of alpha-alkynyl-PMOXA and omega-N-3-P4VP, in which alpha-alkynyl-PMOXA and omega-N-3-P4VP were prepared by cationic ring opening polymerization and atom transfer radical polymerization, respectively. Stable coatings were formed when dropping PAA solution on the top of PMOXA-b-P4VP pre-coatings, due to hydrogen-bonding interaction between P4VP and poly(acrylic acid) (PAA). The long-term stability of these PMOXA-b-P4VP/PAA coatings showed that increasing PMOXA chain length can improve not only the hydrophilicity but also the stability of the coatings. This simple method can form stable coatings on either inorganic (such as, silicon wafer and coverslip) or organic material [such as, poly(methyl methacrylate) sheet] surface. At the same time, for the high-hydratability of PMOXA chains, these crosslinked coatings showed well protein-resistant and platelet/cell-repellent properties, and the antifouling properties and long-term availability were enhanced increasing PMOXA polymerization degree.