In recent years, thanks to the simple and yet efficient design, Micro Electro-Mechanical Systems (MEMS) accelerometers have proven to offer a suitable solution for Structural Health Monitoring (SHM) in civil engineering applications. Such devices are typically characterised by high portability and durability, as well as limited cost, hence resulting in ideal tools for applications in buildings and infrastructure. In this paper, original self-made MEMS sensor prototypes are presented and validated on the basis of preliminary laboratory tests (shaking table experiments and noise level measurements). Based on the well promising preliminary outcomes, their possible application for the dynamic identification of existing, full-scale structural assemblies is then discussed, giving evidence of their potential via comparative calculations towards past literature results, inclusive of both on-site, Experimental Modal Analysis (EMA) and Finite Element Analytical estimations (FEA). The full-scale experimental validation of MEMS accelerometers, in particular, is performed using, as a case study, the cable-stayed bridge in Pietratagliata (Italy). Dynamic results summarised in the paper demonstrate the high capability of MEMS accelerometers, with evidence of rather stable and reliable predictions, and suggest their feasibility and potential for SHM purposes.