Hotel Chocolat's two founders have each made £20m from the luxury confectioner's stock flotation on the Alternative Investment Market.
The firm owns 84 shops, two restaurants, a factory in Cambridgeshire and a cocoa plantation on St Lucia complete with hotel. It raised £55.5m at 148p per share from a listing that put its total value at £167m.
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"We have clear plans to invest further in our British chocolate manufacturing operations, in new stores and in our digital offering," Thirlwell said.
"We welcome our new shareholders and look forward with confidence to the next phase of our growth and development as a listed company."
Thirlwell and Harris launched the brand in 2003, after running a chocolate gifting service together for ten years, and retain a 66.6 per cent stake.
The share issue is a "significant step" considering the retailer has previously shunned traditional methods of raising capital, says The Guardian. In 2010, it started a bonds scheme worth £6.9m, with investors paid in chocolate, not cash.
Hotel Chocolat last year turned down approaches from private equity firms who wanted to buy a stake in the business, says the Telegraph, opting for flotation instead so the founders could remain as "guardians of the brand".
Thirlwell, whose father, Edwin, founded both Mr Whippy and Prontaprint, said the flotation signalled a "renaissance of chocolate companies" after iconic brands Thorntons and Cadbury were sold to overseas owners.
Hotel Chocolat has now overtaken Thorntons as the UK's biggest chocolate retailer.