Saccharides are important tracers in aerosol source identification but results in different areas varied significantly. In this study, six saccharides (levoglucosan, arabitol, glucose, mannitol, inositol, and sucrose) were determined for their emission factors and diagnostic ratios from domestic combustion of typical biomass and coal fuels in Northwest China. Three types of coal (i.e., anthracitic coal, bituminous coal, and briquettes) and five types of biomass (i.e., maize straw, wheat straw, corn cob, wood branches, and wood block) collected from regional rural areas were selected. Overall, the ranking of the fuel types in terms of the emission factor of particulate matter less than 2.5 μm in diameter (PM2.5) was coal < firewood fuel < straw fuel, with a range of 0.14–36.70 g/kg. Furthermore, the emission factor (e.g., organic carbon (OC) levels) of traditional stove-Heated Kang in the Guanzhong Plain differed significantly from that of wood stoves burning the same fuel, which is attributable to differences in the combustion conditions. The combined diagnostic ratios of levoglucosan (LG)/OC and arabitol/elemental carbon can be used to accurately distinguish the source contribution from coal and biomass combustion to atmospheric PM. Estimation of the biomass burning (BB) contribution to PM2.5 had an uncertainty of −2.7% to 41.0% and overestimation of 9.9–28.2% when LG was used as the sole tracer, despite its widespread use in other studies; thus, these estimation methods are inadequate and require improvement. The results also revealed that specialized emission control and clean energy strategies are required for both residential BB and non-BB sources on a regional scale.