High-Throughput Experimentation (HTE) workflows are efficient means of surveying a broad array of chiral catalysts in the development of catalytic asymmetric reactions. However, use of traditional HPLC-UV/vis methodology to determine enantiomeric excess (ee) from the resulting reactions is often hampered by coelution of other reaction components, resulting in erroneous ee determination when crude samples are used, and ultimately requiring product isolation prior to ee analysis. In this study, using four published reactions selected as model systems, we demonstrate that the use of LC-MS, SFC-MS, and selected ion monitoring (SIM) mass chromatography provides a highly accurate means to determine ee of products in crude reaction samples using commonplace, low-cost MS detectors. By using ion selection, co-eluting signals can be deconvoluted to provide accurate integrations of the target analytes. We also show that this method is effective for samples lacking UV/vis chromophores, making it ideal for HTE workflows in asymmetric catalysis.