Rice straw is potentially an appropriate feedstock material for biofuel production, since a huge amount of this postharvest residue is generated every year. The transformation of such agricultural biomass into densified products with a higher energy value and their subsequent combustion is associated with several questions. One of them is that rice straw exhibits a large formation of ash during combustion; thus, it is essential to know the nature of its ash melting behavior. Generally, during the combustion of straw biomass, ash sintering occurs in relatively low temperatures, resulting in the damaging of heating equipment. This negative aspect can be overcome by the addition of calcium-based additives. This paper aimed to study the ash melting behavior at a laboratory scale and to determine the ash melting points of rice straw mixed with calcium carbonate (CaCO3) and calcium hydroxide (Ca(OH)2) in different proportional ratios. The standardly produced ash samples from the rice straw obtained from Cambodia were constantly heated up in a muffle furnace, and characteristic temperatures of ash melting, i.e., shrinkage, deformation, hemisphere, and flow temperature, were recorded. The results showed that increasing the additive ratio did not bring linear growth of the melting temperatures. The addition of 1% CaCO3 showed an optimal positive impact of higher ash melting temperatures, and thus a better ability to abate the sintering of the rice straw ash.