Electroless Ni(P)/electroless Pd/immersion Au (ENEPIG) is a common surface finish in electronic packaging, while the Ni(P) layer increases the impedance of solder joints and leads to signal quality degradation in high-frequency circuits. Reducing the thickness of the Ni(P) layer can balance the high impedance and weldability. In this paper, the interfacial reaction process between ultrathin ENEPIG substrates with different Ni layer thicknesses (0.112 and 0.185 μm) and Sn–3.0Ag–0.5Cu (SAC305) solder during reflow and aging was studied. The bonding ability and reliability of solder joints with different surface finishes were evaluated based on solder ball shear test, drop test and temperature cycle test (TCT), and the failure mechanism was analyzed from the perspective of intermetallic compound (IMC) interface growth. The results showed that the Ni–Sn–P layer generated by ultrathin ENEPIG can inhibit the growth of brittle IMC so that the solder joints maintain high shear strength. Ultrathin ENEPIG with a Ni layer thickness of 0.185 μm had no failure cracks under thermal cycling and drop impact, which can meet actual reliability standards. Therefore, ultrathin ENEPIG has broad prospects and important significance in the field of high-frequency chip substrate design and manufacturing.