High-phosphorus electroless nickel is a widely recognized protective plating for oilfield metallic parts subject to corrosion and wear. In the present investigation, thermally activated diffusion treatment was applied to enhance electroless nickel (10-13 wt.% P) plating adhesion on low-alloy steel (UNS G41400) and reduce the risks of spalling. High-phosphorus electroless nickel (10-13 wt.% P) was applied to a variety of UNS G41400 low-alloy steel test samples as per ASTM B733 that were subsequently heat-treated in air for four distinct temperatures, i.e., 510, 540, 570, and 600 °C for 2-10 h. Following post-plating diffusion heat treatments, the initial amorphous electroless nickel was replaced by Ni3P precipitates dispersed in a crystalline nickel-rich phase, with an average hardness improvement from 500 to 700 HK. An increased atomic interdiffusion (from 400 to 3.5 µm) was observed at plating–substrate interfaces, resulting in enhanced adhesion and reduced susceptibility toward spalling. This improvement in adhesion was measured repeatedly through post-bending crack analyses and subsequently validated by interface microindentation. Along with diffusion across plating–substrate interface, nickel oxide formation on surface by oxidation was observed to grow at quasi-parabolic rate with no detrimental impact on spalling. In all cases, plating adhesion was improved by heat treatments due to the diffusion-controlled formation of a seemingly ductile layer.