This study was investigated the thermal properties of underfill with various epoxy resins using thermal analysis methods such as differential scanning calorimetry (DSC), thermo gravimetry analysis (TGA), dynamic mechanical analysis (DMA) and thermo-mechanical analysis (TMA). And, the adhesion strength of the underfills/FR-4 substrate was evaluated. The glass transition temperature (Tg) of underfill which was composed the cycolaliphatic epoxy resin was lower than that of underfill which was not composed the cycolaliphatic epoxy resin. The thermal degradation of underfill was composed of two processes, which involved chemical reactions between the degrading polymer and oxygen from the air atmosphere. The coefficient of thermal expansion (CTE) of underfill which was composed the cycolaliphatic epoxy resin was higher than that of underfill which was not composed the cycolaliphatic epoxy resin. The excessive curing temperatures caused a weak boundary layer of epoxy resin, which resulted in a deterioration of mechanical properties in the epoxy resin and thus led to poor adhesion property between the underfill/FR-4 substrate.