The zoo was started as a private collection by avid animal collector and breeder, Herbert Whitley, in the grounds of his home Primley House.

It was opened to the public on a number of occasions, originally as Primley Zoological Gardens, and closed twice due to disputes with the tax authorities.

He acquired an increasing number of exotics, including a chimpanzee called Bonny Mary, who appeared in the press as "the cleverest chimp in England".

[6] At opening, the admission was one shilling for adults and sixpence for children, with exhibits including bears, monkeys, zebra, baboons, hyena, and many varieties of bird.

[7] In the month of opening, the park was visited by an officer of the Inland Revenue, who informed Herbert that he should be charging an 'amusement tax' on ticket sales.

[8] Whitley immediately closed the park to the public, posting notices on the entrances, explaining the dispute and naming the justices involved in the case.

[9] Herbert had some history of clashing with authority, having fought the Paignton Urban District over his refusal to allow surveyors to access his land with a view to placing sewage and sanitation works, which he also lost at court and at appeal.

Both he and William were exempt war service on grounds of their health, and when Chessington Zoo needed to evacuate their animals, Herbert agreed to house them at Primley, and so ended up with a large collection.

[7] In 1995, the zoo received £2.9 million from the European Regional Development Fund, allowing major facilities upgrades which lasted until 2001.

[7] This included the building of the Marie Le Fevre ape centre, the new elephant and giraffe house, and the Reptile Tropics attraction.

[21] The zoo has a large collection of around 2,000 animals across over 400 species as of 2011[22] (mammals, birds, reptiles and amphibians) across many different, naturally-themed exhibits.

In January 1939, Whilst back as a private zoo after closing due to the argument with the Inland Revenue, a leopard escaped its enclosure after mauling its keeper, John Hockings.

[24] The animal stayed on zoo grounds,[25] and repeated attempts were made to lure it into a cage trap with meat.

[29] The same zookeeper involved in the leopard incident, John Hockings, was badly mauled by a North American brown bear in 1948 after the then 77 year old failed to secure the safety door between the inner and outer cages during cleaning in December 1948.

Whilst three were quickly rounded up,[35] one wallaby named Sue escaped into the wider zoo grounds, and evaded capture for over two weeks.

[38][39] A sonic boom at around 2am over Paignton in 1961 disturbed the animals and caused a stallion zebra to escape into surrounding woods, where a range of people, including tourists, joined in the hunt.

[44] Three western lowland gorillas escaped from their enclosure into a secure corridor in July 2017, where they were left overnight, during which time they managed to cause thousands of pounds of damage to utility supplies, including water pipes, ducts, and electrical wiring.

[44] Following a closure for bird flu in September 2022, on the first day of reopening, the zoo was evacuated due to the escape of two lar gibbons.

It works with partner zoos and gardens in these organisations on the management of captive breeding and plant conservation programmes for endangered species.