We describe the time-resolved thermal changes in indocyanine green (ICG)–assisted diode laser ablation of dental caries as a potential technique for painless treatment based on the selective photoabsorption and controlled photothermal ablation. Static ablation mode produced a higher temperature rise compared with scanning mode due to localized accumulation of heat. A temperature rise between 45–80 and 70–95 °C was obtained after 20 s that corresponded to 29 and 80 W cm−2, respectively. The temperature of the tooth surface increased by irradiation time, and it behaved linearly up to 70 °C at 29 and 80 W cm−2. A maximum ablation per area of about 0.3 and 0.45 mg cm−2 was achieved after 80 s exposure at 29 and 80 W cm−2, respectively. A statistically significant difference is observed in mean carious teeth weight at various exposure times between low and high irradiances. A thermal penetration depth of 0.8–9 mm is determined for 1–100 s of exposure time. The IR thermal imaging of ICG temperature as a function of exposure time showed a linear increase for 60 s beyond which it deviated. The laser-induced fluorescence spectroscopy indicated that the ICG quality can be altered during the course of irradiation, which in our case, it corresponded to ≈ 78% loss of signal within 23 min of exposure. The caries removal experiment was performed within 100 s corresponding to ≈ 7% loss. We believe that the application of the above-combined technique can be utilized as a monitoring device to control the ablation interaction process. [ABSTRACT FROM AUTHOR]