Polymer‐based hemostatic materials/devices have been increasingly exploited for versatile clinical scenarios, while it is urgently demanded to reveal the rational design/facile approach for procoagulant surfaces through regulating blood‐material interactions. In this work, degradable powders (PLPS) and thermo‐responsive gels (F127‐PLPS) were readily developed as promising hemostatic materials for versatile clinical applications, through tuning blood‐material interactions with optimized grafting of cationic polylysine: the former was facilely prepared by conjugating polylysine onto porous starch particle, whilst F127‐PLPS was prepared by the simple mixture of PLPS and commercial thermo‐sensitive polymer. In vitro and in vivo results demonstrated that PLPS2 with the optimal‐/medium content of polylysine grafts achieved the superior hemostatic performance. The underlying procoagulant mechanism of PLPS2 surface was revealed as the selective fibrinogen adsorption among the competitive plasma‐protein‐adsorption process, which is the foundation of other blood‐material interactions. Moreover, in vitro results confirmed the achieved procoagulant surface of F127‐PLPS through optimal PLPS2 loading. Together with the tunable thermo‐responsiveness, F127‐PLPS exhibited outstanding hemostatic utilization in both femoral‐artery‐injury and renal‐artery‐embolization models. Our work thereby pioneers an appealing approach for generating versatile polymer‐based hemostatic materials/devices.This article is protected by copyright. All rights reserved