In the composite structure of a concrete-filled steel tube (CFST), because the concrete is concealed inside the steel tube, subsurface cavities can occur and are difficult to identify. In this study, a thermal-driven method based on Brillouin fiber-optic sensors (BFOSs) was proposed to quantitatively identify subsurface cavities in CFSTs. By performing a thermodynamic analysis of subsurface cavities in CFSTs, a thermal model related to the relationship between the subsurface cavity size and the temperature rise at the top surface of the CFST was established for the first time. Then, a sensing scheme based on the BFOS was proposed, and its feasibility was evaluated through an experimental program. The experimental program involved the use of an active heating layer for inputting heat flow into the CFST structure and BFOSs for the distributed measurement of temperature to identify subsurface cavities in CFSTs. The experimental results indicated that the BFOSs can achieve real-time distributed measurements of the surface temperature of the CFSTs. According to the temperature anomalies in the temperature rise curves of the CFSTs, the subsurface cavities can be accurately located in the longitudinal direction of the CFST, and its length can be quantified. There is an obvious linear relationship between the temperature rise and the square root of the heating time, from which the equivalent heat absorption coefficient (EHAC) can be determined. Furthermore, according to the relationship between the subsurface cavity height and the EHAC in the thermodynamic theoretical analysis, the subsurface cavity height can be obtained quantitatively.