However, his destiny was changed when, because of his combination of leadership qualities and good knowledge of English, he was chosen as Apostolic Vicar of Calcutta.

Goethals actively encouraged evangelization and education in the Chota Nagpur Plateau of Central India and was an effective help to Constant Lievens's work among the Mundas, Oraons and Kharias in the future state of Jharkhand.

In Calcutta, Archbishop Goethals started a Catholic printing press, establishes several new parishes and gathered a collection of more than 6000 books on India (religions, geography, travels, culture and languages) that became the nucleus of the present Goethals Indian Library and Research Centre (attached to St. Xavier's College, Calcutta).

At one time, he was the president of the Asiatic Society of Bengal, an association of scholars (founded by William Jones) devoted to promoting a better knowledge and appreciation of Indian languages and civilisations.

In 1908 the college received a large collection of rare books, periodical and journals from Archbishop of Calcutta Paul Goethals.