Elemental carbon (EC) content in air is considered a proxy for the diesel exhaust impact at workplaces. This paper examines the possibility of estimating EC content in mine air on the basis of measurements of volatile organic compounds (VOC). The measurement study was carried out in an underground metal mine. Gas chromatography with mass spectrometry (GC/MS) was applied for VOC determination, and thermal-optical analysis (TOA) with an FID detector was utilized for EC measurements. A correlation was found between the measurements of EC and total VOC (TVOC) as well as the content of individual hydrocarbons C12–C14 in the air of an extraction zone in the mine. A regression model was developed which predicts EC based on C12, C13, and C14, considered individually, and the remaining VOCs detected with GC/MS taken in total. The model was statistically significant (p = 0.053), and it offered an EC prediction error of RMSE = 4.60 µg/sample. The obtained result confirms the possibility of using VOC measurements for the preliminary estimation of EC concentrations in mine air. This approach is feasible given the availability of portable GC/MS and offers easy and fast measurements providing qualitative and quantitative information.