Copper complexation with dissolved organic matter (DOM) plays a key role in its toxicity and bioavailability in aquatic environments. Existing speciation models, like the biotic ligand model (BLM) which guide Cu regulations, assume DOM is dominated by humic substances. Meanwhile, research suggests that anthropogenic compounds in wastewater discharge, a significant source of copper to freshwater environments, may be important copper binding ligands. However, their identities remain largely unknown. To address this knowledge gap, we identified and quantified organic copper species isolated from 24-hour composite wastewater samples by solid phase extraction (SPE) using a novel combination of liquid chromatography (LC) with inductively coupled plasma mass spectrometry (ICPMS) and electrospray ionization mass spectrometry (ESIMS). While analyses of samples across different stages of treatment revealed the net removal of Cu (73%) and DOC (66%), LC-ICPMS showed that specific organic-copper complexes persisted and even emerged during treatment. Non-polar complexes decreased in abundance from the initial to secondary treatment stage. In contrast, relatively polar organic Cu complexes, likely formed during treatment, showed a significant increase from the secondary to tertiary stage. Six discrete chromatographically resolved complexes, detected in only wastewater samples, and one detected in both wastewater and a river sample, were identified by LC-Orbitrap MS. These seven molecules that were assigned molecular formulae accounted for about 10% of Cu recovered from SPE. Identification of these compounds provides additional evidence for the formation of new copper-binding ligands during treatment and confirmed the presence of nitrogen and sulfur-containing compounds with strong copper-chelating properties in the wastewater. These findings demonstrate the utility of LCMS approaches for identifying and quantifying distinct organic-copper species in wastewater, as well as tracking their changes and removal during the treatment process.