Self-gelling and bioadhesive powders offered promising effective hemostats to suit irregularly shaped, complex and non-compressible wounds for clinical applications. In the current study, chitosan based polyelectrolyte complex coacervate were simply prepared by mixing high concentrations (10 %) of low molecular weight chitosan (CS) and polyacrylic acid (PAA) solutions. Obtained by lyophilization, the physical cross-linked polyelectrolyte complex powders would form a gel within 5 s upon hydration, which demonstrated excellent mechanical properties, significant antibacterial activities, strong and lasting adhesion on wet tissues in physiological environment. In vitro blood clotting assays showed that the CS/PAA powders could remarkably aggregate blood cells and accelerate blood clotting process. As studied by diverse hemorrhage models, including rat tail, liver and heart injuries and dog incision, CS/PAA powders significantly facilitated the decrease of blood loss as well as hemostatic time by creating robust physical barriers and promoting blood clot formation on the bleeding sites. These outstanding properties in terms of easy preparation, rapid self-gelling, strong wet adhesion, effective hemostasis and shape-adaptability endowed CS/PAA polyelectrolyte complex powders with great potential in managing acute hemorrhage of non-compressible trauma.