In this study, the recovery rates of the dissolution method for radioactivity analysis of expandable polystyrene (EPS) with a liquid scintillation counter (LSC) using tetrahydrofuran (THF), toluene, and acetone as solvents were estimated. The detection efficiency calibration curve for each solvent was derived. Two methods—the volumetric ratio method and the quenching agent method—were used to prepare quench source sets, and calibration curves were derived by linking the data from the two quench source sets. The R2 value of the calibration curve for THF was found to be 0.984. The relationship between the mass of dissolved EPS and the quench level was estimated: the quench level increased as the mass of dissolved EPS increased. Premix and postmix dissolution methods were tested. The recovery rates using THF with the premix method were 84.9 ± 0.9% and 96.5 ± 1.5% for 3H and 14C, respectively. Furthermore, the stability of the recovery rate over time when using THF was evaluated. The dissolution method with the premixed solution exhibited a more stable recovery rate over time. The dissolution methods were found to be applicable for analysis using LSC, and THF was found to be the most suitable solvent for the proposed method.