Bioresources offer essential biological functionality for biomedical applications, yet their clinical translation is limited by a fundamental dilemma: in conventional allogeneic host-to-patient (A-B) designs, stringent pathogen-removal processes often inactivate the very biomolecules that provide function while introducing risks of immunogenicity and contamination. To resolve this, we introduce a ligand dissociation-induced phase-transition strategy to construct hemoglobin-based ultrathin biocoatings, enabling a robust autologous-to-autologous (A-A) route. Mild reductant-initiated redox-triggered assembly enabled hemoglobin directly extracted from the patient's own blood to self-organize into nanoscale films without harsh chemical treatments. This high-efficiency process allows 1 mL of blood to functionalize ∼0.9 m2 of diverse substrates, creating coatings that are not only structurally robust and antibiofouling but also capable of coassembling with heparin. The resulting composite significantly prolongs activated partial thromboplastin time (>600 s) with reduced systemic toxicity while also eliminating cross-individual transmission risk, establishing a clinically translatable paradigm for personalized, blood-contacting medical devices.
Keywords: Biocoating; amyloid-like; anticoagulation; ligand dissociation; surface modification.