The effects of plasma treatment on the surface of the flame resistant-4 (FR-4) substrate with underfills under various treatment conditions (operating gas, operating time, operating power) are investigated by using contact angle measurement, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The plasma treatment on substrate surfaces increased the oxygen containing functional groups or the polar component of the surface free energy, improving the wetting characteristics of the underfills/FR-4 substrates. The plasma treatment conditions which minimised the contact angle between the underfills and FR-4 substrates were an operating power of 300 W and operating time of 180 s under Ar gas atmosphere.