The characteristics of radon exhalation in the hygroscopic properties of powder solid wastes are immensely significant for environmental safety and their transportation, storage, and landfill. This study detected the radon concentration of superfine cement and five kinds of powder solid waste: fly ash, silica fume, coal gangue, S95 mineral powder, and molybdenum tailing powder, at different hygroscopic times for 1–5 d under 95 % relative humidity. Additionally, the influence of particle size and porosity of solid waste on radon exhalation characteristics was analyzed using a laser particle size analyzer and nitrogen adsorption technology. The results show that the radon exhalation rate of the solid waste was at a low level in dry conditions. Although the presence of water due to the increased moisture absorption rate inhibited the radon exhalation to a certain extent, it was higher than that in dry conditions. The reciprocal of the moisture absorption rate had a strong linear relationship with the ratio between the radon exhalation rate after hygroscopy and radon exhalation rate from dry materials. The pore structure has a significant effect on the exhalation rate of radon, and the macropores inhibits the exhalation rate of radon. The results of this study have guiding significance for the reuse of solid waste and the prevention of radiation risk of radon exhalation during transportation.