While solder bumps have been used as the bump structure to form the interconnection during the last few decades, the continuing scaling down of devices has led to a change in the bump structure to Cu-pillar/Sn-Ag micro-bumps. Cu-pillar/Sn-Ag micro-bump interconnections differ from conventional solder bump interconnections in terms of their assembly processing and reliability. A thermo-compression bonding method with pre-applied b-stage non-conductive films has been adopted to form solder joints between Cu pillar/Sn-Ag micro bumps and printed circuit board vehicles, using various pad metal finishes. As a result, various interfacial inter-metallic compounds (IMCs) reactions and stress concentrations occur at the Cu pillar/Sn-Ag micro bumps joints. Therefore, it is necessary to investigate the influence of pad metal finishes on the structural reliability of fine pitch Cu pillar/Sn-Ag micro bumps flip chip packaging. In this study, four different pad surface finishes (Thin Ni ENEPIG, OSP, ENEPIG, ENIG) were evaluated in terms of their interconnection reliability by thermal cycle (T/C) test up to 2000 cycles at temperatures ranging from −55°C to 125°C and high-temperature storage test up to 1000 h at 150°C. The contact resistances of the Cu pillar/Sn-Ag micro bump showed significant differences after the T/C reliability test in the following order: thin Ni ENEPIG > OSP > ENEPIG where the thin Ni ENEPIG pad metal finish provided the best Cu pillar/Sn-Ag micro bump interconnection in terms of bump joint reliability. Various IMCs formed between the bump joint areas can account for the main failure mechanism.