The European diesel fuel standard, EN590, allows a 7% (V/V) biodiesel (FAME) addition to automotive diesel fuel. The allowed addition of renewable diesel (HVO) to fossil diesel is not defined, as long as the properties of the fuel blend still meet the requirements of the standard. However, it is important to analyze the biofuels’ content in diesel fuel blends. In this article, a development procedure of a calibration method for quantification of the HVO and FAME contents in fossil diesel blends using near-infrared (NIR) spectroscopy is presented. The analytical range of quantification of biodiesel content is from 0 to 10% (V/V) and of renewable diesel content from 0 to 20% (V/V). The partial least squares (PLS) regression method for multivariable data analysis and construction of the calibration models were used to create the calibration method. The constructed PLS models obtained prediction results for all diesel fuel blends with root mean square error of prediction (RMSEP) values of 2.66% (V/V) for the HVO content quantification and 0.18% (V/V) for quantification of the FAME content. This article concludes that the calibration method is acceptable for laboratory applications in practice.