The fundamental data of ignition and combustion characteristics of various biodiesel fuels (BDFs) are exhibited for finding the optimal condition in diesel engines. The experimental research has been conducted in a constant-volume vessel with the pre-burn system under diesel-engine conditions. The ignition delays and heat release rates were investigated under different ambient temperatures and pressures. This study used diesel oil and various BDFs such as jatropha methyl ester (JME), coconut methyl ester (CME), soybean methyl ester (SME) and palm methyl ester (PME). The experimental results on fuel-spray development and combustion characteristics were affected by the properties of biodiesel fuels (BDFs), which may support potentially the optimal design of diesel engine fueled with BDFs. Evaporation and mixing are promoted at the tip of fuel jet with lower distillation temperature and lower viscosity, resulting in a shorter length dense region in the spray. These properties may disturb the mixture formation of BDFs at spray tip although the penetration lengths are almost same. The ambient temperature (T_i) and ambient pressure (p_i) strongly influenced the ignition and combustion processes of BDF and diesel oil. Though ignition delays of all BDFs are shorter than that of diesel oil in the whole temperature range from 600 K to 1200 K, CME exhibits the significant shortest delay, suggesting a dominant effect of physical properties of mixing process. At the ambient temperature 800 K and 4 MPa, all of BDFs and diesel oil predict the similar histories of heat release rate. The pre-mixture combustion with longer ignition delay dominates the combustion process at 700 K, but its period is almost constant irrespective of BDF. Ignition delay becomes longer than the injection period for high density and viscosity tested fuels, resulting in a very slow combustion.