Chromium, existing primarily as trivalent (Cr(III)) and hexavalent (Cr(VI)) forms, poses health risks in occupational settings, particularly Cr(VI), a known carcinogen. Workers in industries such as chromate pigment production, chrome electroplating, and welding on chromium-containing metals are at risk of inhaling airborne chromium, leading to respiratory issues and lung cancer. This research aimed to develop and validate an analytical method for quantifying soluble Cr(III), Cr(VI), and total chromium in a single air sample to address health concerns in industrial environments. A method based on EPA Method 6800 Elemental and Molecular Speciated Isotope Dilution Mass Spectrometry was developed for Cr speciation, with a digestion procedure for insoluble chromium compounds, including spinel oxides, without the use of hazardous acids. The quantification limits were 0.3 ηg for soluble Cr(VI), 1.1 ηg for soluble Cr(III), and 0.9 μg for insoluble Cr, well below exposure thresholds. The methods show high precision and accuracy, offering a promising approach for chromium monitoring in workplace air.