The English businesswoman and entrepreneur died in Morocco on Saturday following a long illness, her PR agent confirmed on Sunday.
Several former Dragons from the show including Peter Jones, Theo Paphitis, Deborah Meaden and Duncan Bannatyne have paid tribute to her.
Ms Devey was made a CBE in 2013 for services to the transport industry and to charity.
She was known for appearing on the long-running BBC investing show Dragons' Den before leaving to present the Channel 4 series The Intern.
Fellow 'Dragon' Theo Paphitis paid tribute to Ms Devey, saying: "So sad to hear of the passing of the lovely Hilary Devey.
"She left us all with some fantastic memories, may she rest in peace. My thoughts are with her family."
Peter Jones, who would sit a few seats along from Ms Devey as they grilled prospective business partners, said: "She was an inspiring woman and it was great to spend time with her on Dragons' Den. Sending my deepest condolences to her family."
Deborah Meaden tweeted: "She was unique in every way and brought grit and warmth with her into the Den.
"My thoughts are with her family and loved ones. RIP Hilary. truly one of a kind."
Duncan Bannatyne also commented on the news: "So young. Too young. Rest in Peace Hilary".
Ms Devey made her fortune launching Pall-Ex, a palletised freight network, which grew into an international network with a combined turnover of over £100m.
She appeared on Dragons' Den between 2011 and 2013 alongside fellow investors Peter Jones, Theo Paphitis, Duncan Bannatyne and Deborah Meaden.
Commenting on her role in 2011, Ms Devey said she was proud to "do my part" to support the next generation of UK entrepreneurs "at a time when the banks are failing to invest in British small businesses".
She added: "In order to set-up Pall-Ex in the mid-nineties, I had to sell my house and car to get the start-up capital necessary to fulfil my business ambitions, as none of the banks appreciated my potential.
"I would have loved the opportunity to have stood before the Dragons, and I will remember my own experiences and the realities of running a business today, when choosing to support - or reject - the budding entrepreneurs joining me in the Den."
Her Dragons' Den investments included luxury mattress company Duvalay, run by husband and wife team Liz and Alan Colleran.
Ms Devey also campaigned for various charities including serving as vice president of The Carers Trust, as well as being a patron for The Stroke Association and Fresh Start - New Beginnings.