This article presents a two-step method of iron red synthesis based on waste long-term deposited iron(II) sulfate. The first step is the purification of waste iron sulfate, and then the pigment is synthesized by precipitation using a microwave reactor. The newly developed method of purification allows for quick and thorough purification of iron salt. The use of a microwave reactor in the synthesis of iron red makes it possible to reduce the temperature of the goethite–hematite phase transition from 500 °C to 170 °C and skip the calcination process. A temperature reduction in the synthesis decreases the formation of agglomerates of synthesized materials compared to commercial ones. The results of the research showed a change in the physicochemical properties of the obtained pigments depending on the conditions of synthesis. Waste iron(II) sulfate is a promising raw material for the synthesis of iron red pigments. Laboratory pigments are found to be differ from commercial pigments. The difference in properties speaks in favor of synthesized materials.