The importance of real-time dose evaluation has increased for recent advanced radiotherapy. However, conventional methods for real-time dosimetry using gel dosimeters face challenges owing to the delayed dose response caused by the slow completion of radiation-induced chemical reactions. In this study, a novel technique called photoluminescence-detected pulse radiolysis (PLPR) was developed, and its potential to allow real-time dose measurements using nano-clay radio-fluorogenic gel (NC-RFG) dosimeters was investigated. PLPR is a time-resolved observation method, and enables time-resolved fluorescence measurement. NC-RFG dosimeters were prepared, typically consisting of 100 μM dihydrorhodamine 123 (DHR123) and 2.0 wt.% nano-clay, along with catalytic and dissolving additives. We successfully achieved time-resolved observation of the increase in fluorescence intensity upon irradiation of the dosimeter. Dose evaluation was possible at 1 s after irradiation. The dose-rate effect was not observed for the deoxygenated dosimeter, but was observed for the aerated dosimeter. Besides the dose-rate effect, linear dose responses were obtained for both conditions. Furthermore, we made a novel observation of a decay in the fluorescence intensity over time in the early stages which named fluorescence secondary loss (FSL) and elucidated the conditions under which this phenomenon occurs.