In this article, structured laser illumination planar imaging and polarization ratio techniques are successfully combined to size droplets in various optically dense sprays. The polarization ratio approach is based on the acquisition of the perpendicular and parallel polarized components of Lorenz–Mie scattered light, for which the ratio is proportional to the surface mean diameter, D21. One of the main advantages of this technique, compared to some other laser imaging techniques for particle sizing, is that no fluorescent dye is required. This makes the technique suitable for characterizing sprays under evaporation conditions, such as combustion or spray drying applications. In addition, the SLIPI technique aims at suppressing the detection of multiple light scattering and at extracting the desirable single-light scattering signal. To test the reliability of this novel approach, an industrial hollow-cone nozzle is used, injecting at 50 bar water mixed with Glycerol (in the range of 0–60%). The first aim of this work is to study the experimental parameters that influence the reliability of the technique, such as the polarization orientation of the incident light, the refractive index of the injected liquid and the variation of the droplet size distribution. Using Phase Doppler Anemometry, the results show that a linear calibration is obtained for droplets ranging between 10 and 70 μm, when the incident illumination has a polarization set to 10° and 20°. In addition, this article demonstrates the feasibility of the technique for the measurement of liquids having a refractive index reaching 1.41. In the last stage of this work, after rotating the nozzle every 5°, a 3D tomographic reconstruction of D21 is performed. This demonstrates the robustness and efficiency of the technique for droplet sizing in 3D, under challenging conditions.