The family counting house Hibbert, Purrier and Horton was extensively involved in the shipping and distribution of slave-produced goods, particularly sugar from Jamaica.

As a result, (and also perhaps influenced by his wife's family connections to Huguenot Peter Isaac Thellusson, whose uncle, Sir Ralph Woodford, Governor of Trinidad, was a leading exponent of "free labour" from the East Indies),[7] Hibbert became a leading member of the pro-slavery lobby, and acted as chairman of the Society of West India Merchants.

[6] He gave evidence to the committee of inquiry into the slave trade in 1790, arguing that abolition would ruin the West India interest, and stating that he annually imported produce worth between £200,000 and £250,000 and that he had heavily invested in Jamaica through loans to planters.

A respected botanist and bibliophile, he was a founder of the London Institution in 1805 (vice-president in 1806) and elected a Fellow of the Royal Society in 1811.

According to Loudon, "The collection of heaths, Banksias, and other Cape and Botany Bay plants, in Hibbert's garden, was most extensive, and his flower-garden one of the best round the metropolis.

"[17] Hibbert funded various botanical expeditions, notably that of James Niven, an avid gardener and collector of plants, who was sent to the Cape region of South Africa in 1798.

[7] He remained for five years, sending home a 'valuable herbarium of native specimens' and new plants, including five new species of proteas – Hibbert's passion.

[23] Hibbert lived for some years in London, dividing his time between a house in Portland Place and another, The Hollies, on the north side of Clapham Common[7] in Clapham in south-west London, where he accumulated a considerable collection of books, including Gutenberg's Bible on paper (now at New York), the 1459 Psalter on vellum (now at The Hague) and the Complutensian polyglot, also on vellum (now at Chantilly).

[27][28] Letters to and from Hibbert illustrate the roles he undertook; in certain instances of maritime misfortune he would donate his own money to help those affected.

This was documented in 1825, whereby Thomas Edwards wrote to Hibbert 'to acknowledge the receipt of your donation of the 18th...and...to tell you that this sum of £200...has been dedicated amongst the persons harmed...agreeably to your directions.

[30] Hibbert's payment rewarded the 'brave, bold, athletic' Mr Wright for his efforts in saving lives, and to help him replace the equipment he lost at sea.