It is shown that lithium aggregates promotedthe efficient metalation of phenylpyridines and stabilizationof phenylpyridyllithium. The BuLi−LiDMAE superbaseprevented dimerization or nucleophilic addition encounteredwith t-BuLi or n-BuLi. The reported selective pyridine ringlithiation of 2-, 3-, and 4-phenylpyridine α to nitrogen opensa straightforward access to their derivatives.