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Bi-porous Ti3AlC2 wicks with the controllable pore structure were fabricated with the dissolvable pore former NaCl and cold pressure in this work. The bi-porous structure consisted of fine gap pores (<2 μm) and large pores formed by pore formers (6–12 μm). The NaCl addition increased the porosity and pore size and accordingly widened the pore size distribution. The pore size proportion could be tailored by cold pressure with little change on the porosity. The fine pores proportion increased and the pore size distribution shifted to the small size with the increase in cold pressure. Effects of the pore structure on the capillary performance and compressive strength were also discussed. The capillary performance and compressive strength were dominated by the porosity. The increasing porosity enhanced the capillary performance (ΔPcapK) and reduced the compressive strength. The wick with higher fine pores proportion exhibited better capillary performance and compressive strength when the porosity was similar. The bi-porous Ti3AlC2 wick produced with 30% NaCl addition and cold pressure 20 MPa had the optimal comprehensive performance.