In the production of sulfuric acid, sulfur cake—a waste product of the sulfur purification process—is formed in large quantities, which requires its disposal and use. For its use in composite materials, modification is necessary to convert sulfur into a polymer form. The aim of the study was to develop a method for modifying sulfur cake—a waste product of sulfuric acid production—for its disposal. Available reagents—styrene, glycerol, and oleic acid—were tested as modifiers in the work. The sample compositions consisted of 100% sulfur cake (no. 1) and its mixtures: 97% sulfur cake + 3% styrene (no. 2), 97% sulfur cake + 3% glycerol (no. 3), 97% sulfur cake + 3% oleic acid (no. 4), 95% sulfur cake + 3% styrene, 1% glycerol, and 1% oleic acid (no. 5). Modification of sulfur cake was carried out at a temperature of 140 °C for 30 min. The composition, crystal structure, and thermal properties of the samples of the original and modified sulfur cake were studied using X-ray phase and X-ray structural analyses, IR spectroscopy, differential scanning calorimetry, differential thermal and thermogravimetric analysis. The optimal modifier for sulfur cake was a mixture of styrene, glycerol, and oleic acid, which led to the formation of acetal (polyoxymethylene) and an improvement in the structure due to a decrease in the content of impurities. Modification of sulfur cake with styrene resulted in the appearance of a CAr–S bond band at 571 cm−1, and modification with oleic acid a C–S band in the region of 694 cm−1 in the IR spectra. The results of differential scanning calorimetric analysis showed an increase in the heat of fusion of sulfur by 12.45 J/g in the samples of sulfur cake modified with glycerol and styrene. Modification of sulfur cake with oleic acid and a mixture of reagents resulted in the appearance of a third peak with maxima at 244.2 and 264.0 °C, which demonstrated a significant effect of the indicated additives on the thermal behavior of the sulfur cake. Proposed schemes for modifying sulfur cake with styrene and oleic acid are presented.