In multiphase modeling of fluidized beds, pulverized coal combustors, spray combustors, etc., where different temperatures for gas and solid phases are considered, the governing equations result in separate energy equations for each phase. For high-temperature applications, where radiation is a significant mode of heat transfer, accurately predicting the radiative source terms across each individual phase is an essential task. A spectral photon Monte Carlo (PMC) method is presented here with detailed description of the implementation features, including the spectral treatment of solid particles, random number correlations, and a scheme to split emission and absorption across phases. Numerical results from the PMC method are verified against direct numerical integration of the radiative transfer equation (RTE), for example, problems including a cylindrically enclosed homogeneous gas-particulate medium and a simple fluidized bed example. The PMC method is then demonstrated on a snapshot of a pulverized-coal combustion simulation.