Rolin excelled in the Gymnasium of Ghent and his musical skills quickly became apparent. At age 16 he travelled to the United Kingdom and thence to Paris, where he received a first prize at the Lycée Charlemagne. He then returned home and studied law at the University of Ghent. After graduating, he followed his father's example and went to Berlin for further studies. In 1860, when he was 25 years old, he was offered the chair of modern political history, but declined to help his father in his law firm.