To investigate the effects of different alcohol additives in biodiesel fuel on the spray, combustion characteristics, and soot formation and oxidation, a detailed comparative study between the butanol-biodiesel blend and the ethanol-biodiesel blend was carried out in an optical constant volume combustion chamber. Two different volumetric blend fuels were tested in this study with different ambient temperatures at the start of injection (from 800 to 1200 K). The volumetric ratios were the 20% butanol/80% soybean biodiesel referred to as B20S80 and 20% ethanol/80% soybean biodiesel referred to as E20S80. Results demonstrated that the microexplosion occurred for B20S80 and E20S80 fuels at 800 and 900 K ambient temperature because of the volatility difference between the additives (butanol or ethanol) and the base fuel (biodiesel). The E20S80 fuel presented higher peak pressure and. shorter combustion duration compared to the B20S80 fuel. The autoignition was earlier for the B20S80 fuel at 1000 and 1200 K ambient temperature, while the autoignition of the B20S80 and E20S80 fuels was nearly the same at 800 K ambient temperature. The E20S80 fuel had a lower flame luminosity compared to the B20S80 fuel. The soot distribution was increased downstream of the spray jet with a higher ambient temperature for both tested fuels, and E20S80 had a lower value of normalized time-integrated soot mass (NTISM). Therefore, E20S80 has more advantages to reduce the soot emission compared to the B20S80 fuel. Also; increasing the ambient temperature from 800 to 1200 K led to a rapid increase in the value of NTISM for both tested fuels. Therefore, a lower, ambient temperature with the piston at top dead center (TDC) should have more advantages to combustion and soot control in a real diesel engine.