In comparison to Li-ion batteries, Na-ion batteries offer the benefits of low cost, good low-temperature performance, and safety, attracting great attention in the cost- and reliability-sensitive applications. With high capacity and low cost, Prussian blue-like materials (PBAs) stand as promising cathode materials for Na-ion batteries. However, the presence of crystalline water within their structure induces fast performance decay of the battery, serving as a critical bottleneck limiting their application. This work reports a facile thermal treatment strategy to effectively remove crystalline water from PBAs cathode materials, improving capacity retention from 73% to 88% after 340 cycles. The in-situ analysis uncovers that the initial loss of Coulombic efficiency of PBAs cathode is a result of its irreversible transformation from a trigonal form to cubic phase during the charging and discharging process. This issue can be addressed by introducing of Na₂C₂O₄ to compensate the irreversible Na loss in the cathode. On this basis, a high-performance quasi-solid-state Na-ion battery is built by pairing a low-water-content PBAs cathode with Na₂C₂O₄ additive and a hard carbon (HC) anode within a poly(ethylene glycol) diacrylate (PEGDA)-based quasi-solid-state electrolyte with high ionic conductivity and electrochemical stability. This battery exhibits the specific capacities ranging from 58 to 105 mAh·g^-1 at current densities from 20 to 500 mA·g^-1, capable of sustaining stable cycling for over 200 cycles. This study underscores the significant improvement in stability and capacity of PBAs cathode materials by the efficient removal of crystalline water in them.