This study assessed the emissions of gaseous pollutants and particle size distributed water-soluble organics (WSO) from a diesel vehicle fuelled with ultralow sulphur diesel (B0) and 10 (B10), 20 (B20), and 30% (B30) biodiesel blends in a chassis dynamometer tested under transient mode. Particulate emission sampling was carried out in an ultraviolet (UV) test chamber using a 10-stage impactor. Samples were grouped into three size fractions and analysed by gas chromatography-mass spectrometry. Increasing the biofuel ratio up to 30% in the fuel reduced WSO emissions by 20.9% in comparison with conventional diesel. Organic acids accounted for 82–89% of WSO in all tested fuels. Dicarboxylic acids were the most abundant compound class, followed by hydroxy, aromatic, and linear alkanoic acids. Correlations between compounds demonstrated that adding biodiesel to diesel fuel reduces the emissions of nitrogen oxides (NOx), benzene, toluene, ethylbenzene and xylenes (BTEX), methane (CH4), total and nonmethane hydrocarbons (THC and NMHC), and dicarboxylic and hydroxy acids, but increases emissions of carbon dioxide (CO2) and alkanoic and aromatic acids. Emissions of dicarboxylic and hydroxy acids were strongly correlated with the biodiesel content. WSO emissions of coarse and fine (1.0–10 μm) particles decreased with the increasing biofuel content in fuel blend. The total share of ultrafine (0.18–1.0 μm) and nanoparticles (< 0.18 μm) increased in WSOs emissions from B20 and B30 blends, when compared with petrodiesel. The biodiesel content also affected the chemical profile of WSO size fractions.Supplementary InformationThe online version contains supplementary material available at 10.1007/s11356-023-26819-3.