Electroless copper plating process of N, N, N′, N′-tetrakis (2-hydroxypropyl)ethylenediamine(THPED) chelating agent was researched comprehensively. The results indicate that plating rate decreases with the 3H2O has a bad effect on deposits quality, but 2, 2′-dipyridyl and PEG make deposits quality improve greatly. Low concentration of 2-mercaptobenzothiozole (2-MBT) increases plating rate and improves deposits quality, but decreases plating rate and worsens deposits quality when 2-MBT reaches 5 mg/L. The optimal conditions of this electroless MBT are 16.8 g/L, 16.0 mL/L, 13.3 g/L, 0.5 g/L, 5.0 mg/L and 2.0 mg/L, respectively, pH value is 12.75,bath temperature is 30 ℃. Plating rate reaches 9.54 μm/h plating for 30 min in the bath. The SEM images demonstrate that the surface of copper film is smooth and the crystal is fine.