Signal Amplification by Reversible Exchange (SABRE) is a relatively simple and fast hyperpolarization technique that has been used to hyperpolarize the α‐ketocarboxylate pyruvate, a central metabolite and the leading hyperpolarized MRI contrast agent. In this work, we show that SABRE can readily be extended to hyperpolarize 13C nuclei at natural abundance on many other α‐ketocarboxylates. Hyperpolarization is observed and optimized on pyruvate (P13C=17%) and 2‐oxobutyrate (P13C=25%) with alkyl chains in the R‐group, oxaloacetate (P13C=11%) and alpha‐ketoglutarate (P13C=13%) with carboxylate moieties in the R group, and phenylpyruvate (P13C=2%) and phenylglyoxylate (P13C=2%) with phenyl rings in the R‐group. New catalytically active SABRE binding motifs of the substrates to the hyperpolarization transfer catalyst—particularly for oxaloacetate—are observed. We experimentally explore the connection between temperature and exchange rates for all of these SABRE systems and develop a theoretical kinetic model, which is used to fit the hyperpolarization build‐up and decay during SABRE activity.