The pyridylation of alkynes with pyridylboronic acids is realized under rhodium catalysis. Chemodivergent pyridylation products, including alkenylpyridines produced via the hydropyridylation pathway and cyclopenta[c]pyridines produced via the pyridylation/cyclization pathway, were selectively produced by fine-tuning the reaction conditions. A mechanistic study revealed that 1,4-rhodium migration to the pyridine ring was involved as the key step in the chemodivergent synthesis.