Already interested in the new hobby of stamp collecting, he started to trade in stamps in 1856 from a desk in his father's shop. He began trading as E. S. Gibbons, then as E. Stanley Gibbons, and later as Stanley Gibbons & Co. A lucky deal in 1863 caused his business to take off: he bought two sacks of Cape of Good Hope triangular stamps for £5 from two sailors who had won them in a raffle in Cape Town. He later claimed to have made £500 on the deal. In November 1865 he issued a sixteen-page price list and catalogue, the forerunner of Gibbons'scatalogues.
On his father's death in 1867 Gibbons took over the chemist's business, and in the 1871 census he was described as 'chemist and dealer in foreign stamps'. He sold the chemist's business in 1872 and moved to new premises at Plymouth Hoe. Here he published his first Gibbons ‘V.R.’ stamp album, followed by the ‘Improved’ and illustrated ‘Imperial’ albums.
Gibbons was married five times
(Source GE Dixon)