To provide a scientific basis for the resource utilization of chromium slag, this article studies the release law of hexavalent chromium in the aged calcium-free chromium slag. XRD (X-ray diffractometer) and MLA (Mineral Liberation Analyzer) were used to analyze the composition of the chromium slag; using sulfuric acid-nitric acid as the leaching solution, the release law of hexavalent chromium in chromium slag and the leaching kinetics were studied. The results show that main components of the chromium slag are magnesioferrite, chromite, hematite, hydrargillite, and spinel; chromium is mainly present in chromite and magnesioferrite; the leaching rate of hexavalent chromium increases with the increase of temperature or the decrease of pH. The analysis of leaching kinetics shows the leaching rate is controlled by the internal diffusion reaction, and the apparent activation energy is 11.93 kJ·mol–1. The chromium slag is aged in high temperature seasons, which is conducive to the precipitation of hexavalent chromium in the chromium slag, can increase the yield of chromate in the roasting kiln, and is conducive to resource utilization; chromium slag should be stored in order to prevent acid rain erosion which leads to environmental pollution risk (e.g. drinking water).