This paper aims to present an experimental investigation on the behavior of web-flange junctions (WFJs) rotational stiffness of pultruded fiber-reinforced polymer composites (FRP). Channels and I-sections were tested using a simple set-up, which was developed in order to experimentally characterize the junctions in a direct manner. The Digital Image Correlation (DIC) technique was used, allowing overall deflections and relative rotations between web and flange to be monitored. The WFJs' imperfections were analyzed through an optical microscope and correlated with the cracks' formation. Further, damage thresholds are identified using available stress equations for curved composite members and lower bound functions are proposed to simulate the junction stiffness retention. Finally, two Equations are developed in order to analytically predict pultruded junctions' rotational stiffness per unit of width. In general, the theoretical and experimental results agreed fairly well, with a maximum difference of 24% for I-sections and 38% for channels.