We present a study on the oxidation of isoprene under several different conditions that may model both atmospheric and combustion chemistry. Anions, formed by passing isoprene/oxidant gas mixtures through a pulsed discharge generating a range of species, are separated via mass spectrometry and characterized by anion photoelectron (PE) spectroscopy supported by computations. Specifically, a UV-irradiated isoprene/O2 mixture, which additionally produces O3, and an isoprene/O2/H2 mixture, which generates •OH when passed through the discharge, were sampled. The mass spectra of ions generated under both conditions show the production of intact molecular ions, ion-molecule complexes (e.g., O2-, O4-, and O2-·isoprene), and singly deprotonated species (e.g., deprotonated isoprene, C5H7-). In addition, both smaller and oxidized fragments are observed using both gas mixtures, though relative abundances differ. From the UV-irradiated isoprene/O2 gas mixture, additional intact molecular products of reactions initiated by ozonolysis of isoprene, methylglyoxal, and dimethylglyoxal were observed. Fragmentation and oxidation of isoprene observed in both gas mixtures included species with m/z 39, 53, 67, 69, and 83 that we attribute to a series of alkyl- and alkenoxide-based anions. The coexistence of intact molecules and complexes with fragments and reaction products demonstrates the versatility of this ion source as a simple and efficient anion formation method for studying species that may be relevant in atmospheric and combustion chemistry.