AbstractOxidation of isoprene by nitrate radicals (NO₃) or by hydroxyl radicals (OH) under high NO_x conditions forms a substantial amount of organonitrates (ONs). ONs impact NO_x concentrations and consequently ozone formation while also contributing to secondary organic aerosol. Here we show that the ONs with the chemical formula C₄H₇NO₅ are a significant fraction of isoprene‐derived ONs, based on chamber experiments and ambient measurements from different sites around the globe. From chamber experiments we found that C₄H₇NO₅ isomers contribute 5%–17% of all measured ONs formed during nighttime and constitute more than 40% of the measured ONs after further daytime oxidation. In ambient measurements C₄H₇NO₅ isomers usually dominate both nighttime and daytime, implying a long residence time compared to C₅ ONs which are removed more rapidly. We propose potential nighttime sources and secondary formation pathways, and test them using a box model with an updated isoprene oxidation scheme.