Williams' father James was gardener to Robert Warner, the botanist, at Hoddesdon, and Benjamin began working under his father at the age of fourteen. He first gained prominence as an orchid grower when he was hired by the orchid collector C. B. Warner, whose orchids soon began winning prizes at top orchid shows.[{{cite book|author1=Robert Warner (F.R.H.S.)|author2=Benjamin Samuel Williams|author3=Thomas Moore |author4=Henry Williams |author5=William Hugh Gower|title=The Orchid Album, Comprising Coloured Figures and Descriptions of New, Rare, and Beautiful Orchidaceous Plants|url=https://books.google.com/books?id=F40UAAAAYAAJ&pg=PT14|year=1891|publisher=B. S. Williams|pages=14–}}] Williams was a business partner of Robert Parker's in a nursery at Seven Sisters Road in Holloway between 1854 and 1861, and later moved to the nearby Victoria and Paradise Nurseries.[{{Cite web |url=http://www.georgeglazer.com/prints/nathist/botanical/warnerorch.html |title=George Glazer Gallery - Antique Botanical Prints - Orchid Album: J.N. Fitch - B.S. Williams - R. Warner |access-date=2008-02-22 |archive-url=https://web.archive.org/web/20080407210112/http://www.georgeglazer.com/prints/nathist/botanical/warnerorch.html |archive-date=2008-04-07 |url-status=dead }}]
He is buried on the eastern side of Highgate Cemetery.
This botanist is denoted by the author abbreviation B.S.Williams when citing a botanical name.[{{cite book|last = Brummitt|first = R. K.|author2=C. E. Powell|title = Authors of Plant Names |publisher = Royal Botanic Gardens, Kew |year = 1992 |isbn = 1-84246-085-4}}]
