Sodium iron hexacyanoferrate (NaFeHCF) has been recognized as a promising Prussian blue analogue (PBA)-based electrode for electrochemical desalination; however, its application potential is limited by its unsatisfactory desalination capacity and cycling stability. Herein, the structurally distorted high-quality monoclinic NaFeHCF with fewer defects in the framework was synthesized by a crystal-controlled coprecipitation method via tuning the crystallization reaction conditions and applied to seawater desalination. Physicochemical characterization and desalination experiments show that the NFHFC-2 with minimized defects possesses enhanced electrochemical activity of Fe2+ and electrochemical kinetics, thus achieving higher desalination performance (specific capacity of 75.0 mA h g-1 and capacity retention of 85.3% after 50 cycles). Furthermore, a symmetrical NFHCF-2 RCDB is assembled, and the operation parameters (including various salinities and electrode spacing) are optimized to achieve a remarkable salt removal capacity (SRC) of 108.9 mg g-1 and a salt removal rate (SRR) of 2.22 mg g-1 min-1 with low energy consumption (0.056 kW h kg-1-NaCl) and outstanding cycling stability (almost no capacity attenuation in 150 cycles). Impressively, the RCDB further exhibits favorable technical feasibility in the simultaneous removal of univalent/bivalent ions from the natural seawater. This study inspires the design of high-quality PBA-based electrodes with optimized crystal structures for electrochemical desalination.