This paper presents an experimental application of Distributed Optical Fiber Sensors (DOFS) for the Structural Health Monitoring (SHM) of concrete structures affected by internal swelling pathologies. In the framework of a large research project aiming to assess the possible extension of the operating lifetime of nuclear power plants from 40 to 60 years, massive blocks were cast from reactive concrete mixtures intended to develop delayed ettringite formation and alkali–silica reaction. These blocks were subjected to specific ageing conditions to initiate and accelerate the concrete pathologies. Some of the blocks were instrumented with DOFS bonded to the surface and embedded in the concrete. Using an interrogator device based on Rayleigh backscattering and a suitable procedure to eliminate temperature effects, distributed strain measurements were then performed at different time intervals. The first results of this ongoing study made it possible to demonstrate the feasibility and effectiveness of this sensing technology for detecting and monitoring expansion induced by swelling pathologies in representative-scale concrete structures.