Dose-rate monitoring instruments are indispensable to protect workers from the potential risk of radiation exposure, and are commonly calibrated in terms of the ambient dose equivalent (H*(10)), an operational quantity that is widely used for area monitoring. Plastic scintillation detectors are ideal equipment for dosimetry because of their advantages of low cost and tissue equivalence. However, these detectors are rarely used owing to the characteristics caused by low-atomic-number elements, such as low interaction coefficients and poor gamma-ray spectroscopy. In this study, we calculated the G(E) function to utilize a plastic scintillation detector in spectroscopic dosimetry applications. Numerous spectra with arbitrary energies of gamma rays and their H*(10) were calculated using Monte Carlo simulations and were used to obtain the G(E) function. We acquired three different types of G(E) functions using the least-square and first-order methods. The performances of the G(E) functions were compared with one another, including the conventional total counting method. The performance was evaluated using 133Ba, 137Cs, 152Eu, and 60Co radioisotopes in terms of the mean absolute percentage error between the predicted and true H*(10) values. In addition, we confirmed that the dose-rate prediction errors were within acceptable uncertainty ranges and that the energy responses to 137Cs of the G(E) function satisfied the criteria recommended by the International Commission.