Coal ash inevitably forms deposits as combustion residue on the walls and heat transfer surfaces of coal-fired boilers. Ash deposits decrease the boiler efficiency, reduce the generating capacity, and cause unscheduled outages. The radiative heat transfer is the major heat transfer mechanism in utility boilers; thus, the ash deposit emissivity is critical to boiler efficiency and safety. This paper presents a radiative transfer model to predict the spectral emissivities of coal ash deposits. The model includes the effects of the microstructure, chemical composition, and temperature. Typical ash deposit microstructures are generated using diffusion-limited aggregation (DLA). The radiative properties are then calculated using the generalized multiparticle Mie-solution (GMM). The combined GMM and DLA model predicts spectral emissivity better than the original Mie theory and Tien's dependent scattering theory with the average relative difference between predicted results and experimental data decreasing from 17.8% to 9.1% for sample 1 and from 18.6% to 4.2% for sample 2. Maxwell-Garnett (MG) effective medium theory is used to calculate the ash deposit optical constants based on the chemical compositions to include the effect of chemical composition. Increasing temperatures increase the particle diameters and particle volume fractions and, thus, the spectral emissivities. The spectral emissivity ultimately remains constant and less than one. The homogeneous slab model gives the upper limit of the ash deposit spectral emissivity.