This paper describes the development and characterization of isotropically conductive adhesives (ICAs) incorporating copper (Cu) powders as electrically conductive fillers, along with a silane coupling agent for oxidation protection of copper powders, for environmentally friendly, low cost and high thermal reliability applications in microelectronics packaging. The effect of silane coupling agent materials and concentration on the electrical conductivity, thermal stability and reliability of Cu-filled ICAs was investigated for potential alternatives of conventional silver-filled ICAs. The surface characteristics of silane thin films on copper surfaces, such as their hydrophobicity and thermal stability, were also evaluated to compare the performance of antioxidant behaviors of different silane coupling agents for Cu-filled ICAs. The low contact resistance and high thermal stability of the contact resistance of Cufilled ICAs were achieved by addition of an optimized silane coupling agent. Greater thermal stability and improved reliability of Cu-filled ICAs under high temperature and humidity conditions were achieved with a silane coupling agent of high molecular weight and hydrophobicity. The bulk resistivity of~10-4 Xcm of Cu-filled ICAs was achieved with bimodal filler loading.