Abstract: Biodiesel has emerged as a suitable alternative to mineral diesel in compression ignition (CI) engines in order to ensure global energy security and to reduce engine out emissions in near future. Biodiesel derived from various feedstocks available worldwide fits well in the current fuel supply arrangement for transport sector. However, biodiesel as an alternative transportation fuel has been extensively investigated because of differences in its important fuel properties compared with baseline mineral diesel. Since fuel properties greatly influence spray development, combustion, and emission formation in internal combustion (IC) engines, a number of experimental and computational studies on biodiesel usage in CI engines have been performed to determine its brake thermal efficiency (BTE), gaseous emissions, durability, etc., by various researchers using variety of engines and feedstocks. In the present paper, a critical review of the effect of biodiesel's fuel properties on engine performance, emissions, and combustion characteristics in existing diesel engines vis-a-vis conventional diesel has been undertaken. In addition, the progress and advances of numerical modeling involving biodiesel are also reviewed to determine the effect of fuel properties on spray evolution and development of reaction mechanisms for biodiesel combustion simulations. Fuel properties are discussed in two categories: physical and chemical properties, which are key parameters affecting spray and combustion processes. Subsequent sections review spray, combustion, emissions, and performance characteristics of biodiesels under various engine operation conditions. In the last section of this review paper, numerical modeling of biodiesel covering recent numerical models and schemes to understand the behavior of biodiesel combustion and pollutants formation is included. This review paper comprehensively summarizes biodiesel fuel's (BDFs) spray, combustion, and emission characteristics using experimental and numerical approaches. Limitations and scope for future studies are discussed in each section.