Currently, several transport and fuel production sectors are aiming to develop new technologies that can replace traditional fossil fuels by fuels produced from renewable sources, most of them dubbed as Biofuels. In the particular case of n-butanol, an additive widely used in the blend with diesel oil, it has achieved considerably good results; however, the dependence on fossil fuels still remains present. In this investigation, in order to replace diesel oil in CI engines; n-butanol was tested as an ignition improver when blended with ethanol (Biofuel) as energy source. For this purpose, a rapid compression machine (RCM) was used under different test conditions, such as compression ratio from 16:1 to 24:1. The combustion process of Ethanol / n-butanol blend (10% w/w) was compared to a diesel S10 (as baseline fuel) and with mixture of ethanol / polyethylene-glycol 400 (13% w/w) and showed interesting results. These results were discussed and showed the necessity of several modification in the fuel and the compression ignition system in order to burn the mixture of Ethanol / n-butanol.