In recent years, improving the surface properties of large-scale insulation by plasma modification has attracted extensive attention with the development of power systems and high-tech industries. However, routine evaluations of the modification effect and uniformity require complicated tests after the plasma is powered off, which waste a lot of time and cannot regulate the modification effect online. In this study, a novel fluorescence-assisted dielectric barrier discharge (DBD) for fabricating a functional film is developed, and a rapid evaluation method of the modification effect and uniformity is proposed based on fluorescence coloring and image processing technologies. The results show that the addition of an organic fluorescent agent in the DBD with hexamethyldisiloxane (HMDSO) has no negative effect on the plasma discharge and modification effect, and the fluorescence-assisted DBD successfully fabricates the functional films with typical chromogenic groups (N−H and S�O) that exhibit typical fluorescence under an UV lamp. According to image processing and parameter extraction, the plasma-assisted fluorescent film is converted into a two-dimensional (2D) color map with nine color levels, and three characteristic parameters are proposed to evaluate the modification effect rapidly and directly. It shows that the warmer the color of the treated sample, the better the hydrophobicity and electrical insulating properties, where the red region represents the optimally modified surface, while the blue region represents the worst one. The area, shape, and integrity of the plasma modification are clarified quantificationally, which provides the possibility of further online evaluation of the modification effect and uniformity by the plasma treatment.