In 1831, Bayley matriculated at Amherst College, studying there for two years. A classmate later recalled that he "sustained good rank as a scholar" and "possessed decided talent." There, he became an active member of the Alexandrian Literary Society, in which he was given an opportunity to practice public speaking as a participant in its debates. After leaving Amherst, Bayley matriculated in the fall of 1833 at Washington College in Hartford, Connecticut, a young institution with only seven undergraduates in Bayley's senior class. Shortly after his matriculation at Washington College, Bayley became a member of another literary society, the Athenaeum, and during his years there, he helped found a literary and social society, the I.K.A. Bayley's final examinations lasted twenty hours, distributed as follows as recorded by Bayley in a notebook: four hours devoted to the classics—Livy, Cicero, Homer, Tacitus, Juvenal; seven to mathematics and natural science, including navigation, surveying, conic sections, mechanics, chemistry, astronomy, and optics; three to moral and intellectual philosophy and political economy; four to "belles-lettres" and rhetoric; and one each to jurisprudence (James Kent's "Commentaries on American Law") and to Christian evidences (William Paley's). Bayley received his bachelor's degree on August 6, 1835. He had decided to follow in the footsteps of his father and grandfather by studying medicine.