Developing a facile strategy which enhances the structural stability and air/moisture stability of transition metal phosphides for practical applications is important but challenging. Herein, we designed a densely packed free-standing film consisting of carbon-coated FeP nanoparticles anchored on P-doped graphene (FeP@C@PG film) through solventless thermal decomposition and the roll-press method. Phytic acid serves a multifunctional role as both a phosphorus source to prepare ultrafine FeP nanoparticles and a protective layer to improve air stability along with hydrophobic graphene and maximize the utilization of phosphide. This structure can enhance electron/ion transport kinetics, allowing for full utilization of active materials, and buffer large volume expansions while preventing pulverization/aggregation during cycling. Noticeably, the densely packed structure can greatly enhance oxidation resistance by effectively blocking the penetration of air/moisture. Therefore, the FeP@C@PG film delivers a stable reversible capacity of 536.6 mA h g-1 after 1000 cycles at 1 A g-1 with good capacity retention, an excellent rate capability of 440.7 mA h g-1 at 5 A g-1, and excellent oxidation stability at 80 °C in air. Furthermore, a pouch-type full-cell exhibits excellent rate/cycling performance and bendability. This study provides a new direction for the rational design and practical applications of advanced P-based materials used in alkali metal-ion batteries.