The aim of this research work is to study the behaviour of Fiber Bragg Grating (FBG) sensors to interpret their response more accurately in a structural monitoring system. In the presence of a complex stress state, a structure is subjected to strain fields in multiple directions simultaneously and the sensors used for its structural monitoring are affected as well. However, the traditional procedure to calibrate FBG sensors consists of uniaxial tensile tests to calculate a strain sensitivity factor (K) that relates the sensor response to the strain measured during the test. In this study, a polyimide coated FBG sensor is embedded in a cruciform composite specimen to analyse its response to biaxial strain states. The experimental methodology has consisted of carrying out a campaign of biaxial tests on this specimen in which the longitudinal strain (εx) has been kept constant and the transverse strain (εy) has been varied by means of a triaxial testing machine to reproduce different plane stress states. Biaxial tests have allowed to study experimentally the influence of the εy on the longitudinal measurement of the FBG sensor and therefore on the calibration procedure. Finally, the experimental results obtained in both uniaxial and biaxial tests have been compared to the strain-optic theory.