The thermogravimetric characterization and gas emission properties during the pyrolysis of rice husk (RH) and rice straw (RS) were compared, and the properties of waste rice husk ash (RHA) and rice straw ash (RSA) from the combustion process were investigated. The results showed that the pyrolysis of RH and RS followed a four-step mechanism. Comparing the emission properties of small molecule bio-syngas in the pyrolysis of these two biomass wastes implied that RS was more suitable for use as feedstock for thermochemical conversion. Chemical and phase analysis results indicated that the RSA was rich in K, Ca, and P and had good potential for use as a soil amendment or as a material for silicate ceramics. The RHA was rich in SiO2 and could be an ideal silica source for silicon compound preparation or a pozzolan source for blended cement concrete production. Morphology analysis on the ash samples revealed that the high content of alkali metals may cause the higher agglomeration tendency of RSA with respect to RHA. The contrast in pore properties of biomass char wastes isolated from the ashes indicated that the char wastes recovered from RHA would be better used as a low-cost precursor in activated carbon production.