Electroless Ni–P coatings are widely used for corrosion and wear protection, yet their ability to deliver water-based superlubricity and the role of phosphorus content remain insufficiently understood. Here, electroless Ni–P coatings with four P contents (3.4, 6.4, 9.0, and 12.4 wt%) were deposited on GCr15 steel with nearly constant thickness and comparable initial roughness, and were tested against Si₃N₄ balls in neutral 0.5 M NaH₂PO₂ solution. Friction measurements, together with surface topography characterization and tribofilm analysis, were used to link P content with tribofilm chemistry and superlubricity. All coatings achieved macroscale superlubricity, exhibiting steady-state friction coefficients below 0.01, while the running-in time decreased markedly as P content increased. During sliding, the wear tracks underwent mechano-chemical polishing to Sa ≈ 11–12 nm and formed phosphate–silicate tribofilms enriched in P–O and Si–O species on both the coating and the counterface. These findings establish a composition–tribofilm–superlubricity relationship in the Ni–P/NaH₂PO₂ system and demonstrate that P-content optimization is an effective internal design lever to accelerate running-in, mitigate wear, and achieve robust superlubricity under neutral aqueous lubrication.