The development of a piezoresistive coating produced from dispersing graphene nanoplatelets (GNPs) inside a commercial water-based polyurethane paint is presented. The feasibility of its exploitation for realizing highly sensitive discrete strain sensors and to measure spatial strain distribution using linear and two-dimensional depositions was investigated. Firstly, the production process was optimized to achieve the best electromechanical response. The obtained materials were then subjected to different characterizations for structural and functional investigations. Morphological analyses showed a homogenous dispersion of GNPs within the host matrix and an average thickness of about 75 µm of the obtained nanostructured films. By several adhesion tests, it was demonstrated that the presence of the nanostructures inside the paint film lowered the adhesion strength by only 20% in respect to neat paint. Through electrical tests, the percolation curve of the nanomaterial was acquired, showing an effective electrical conductivity ranging from about 10−4 S/m to 3.5 S/m in relation to the different amounts of filler dispersed in the neat paint: in particular, samples with weight fractions of 2, 2.5, 3, 3.5, 4, 5 and 6 wt% of GNPs were produced and characterized. Next, the sensitivity to flexural strain of small piezoresistive sensors deposited by a spray-coating technique on a fiberglass-reinforced epoxy laminate beam was measured: a high gauge factor of 33 was obtained at a maximum strain of 1%. Thus, the sensitivity curve of the piezoresistive material was successively adopted to predict the strain along a multicontact painted strip on the same beam. Finally, for a painted laminate plate subjected to a mechanical flexural load, we demonstrated, through an electrical resistance tomography technique, the feasibility to map the electrical conductivity variations, which are strictly related to the induced strain/stress field. As a further example, we also showed the possibility of using the coating to detect the presence of conducting objects and damage.