Frampton-Calero left Havas Media Group as chief executive of UK and Ireland in October last year.
His appointment with Tink Labs is effective immediately and he will report to Terence Kwok, founder and chief executive of Tink Labs.
He will focus on developing the revenue streams in hospitality, ecommerce, and advertising being opened up by Tink's smartphones, which are branded Handy.
"When I left Havas, I said I wanted to get closer to the digital economy," Frampton-Calero told Campaign. "I've been advising start-ups over the years and have a passion about tech and new early-stage businesses. So when I went through the process of trying to work out what was important to me, I knew I wanted to be part of a fast-growth tech-led product."
Tailored to hotels and their guests, Handys offer free unlimited internet access, integrated services with the hotel, free local and international calls as well as city guides and travel deals.
The devices are now present in 82 countries around the world, covering more than 650,000 hotel rooms, 35,000 of which are in the UK and Ireland.
Tink Labs was founded six years ago and in September 2016 raised US$125m (£93m) in funding that valued it over US$500 million. According to Bloomberg, the company is on track to become Hong Kong's first US$1bn tech 'unicorn'.
"Paul is a proven leader with track record and extensive experience in growing businesses, building brands and mapping customer journeys across multiple touch points," Kwok said. "His passion in the start-up community and the entrepreneurial space makes him the perfect fit for Tink Labs."
The opportunity to join a business that is "reimagining the US$8bn global hospitality industry" was too good to pass up, Frampton-Calero said.
"My immediate goal at Tink Labs is to help the business grow and mature in the region, improve the customer experience and build advocacy and awareness for handy," he added. "There is immense potential with the technology and I am excited at the opportunity to work with the talented team in London, Hong Kong and across the world to take the company forward."