Zoe's Hardest Road Home will see the Strictly Come Dancing It Takes Two host cycle from Blackpool, where she spent the first years of her life living in Thornton, to her current home of Brighton on the south coast.
Ahead of her departure, Zoe said: "I'm feeling every kind of emotion you can image. Fear, anticipation and a very flippy tummy.
"I just want to get going now. All of this talk, all of this training all of this and now I just want to get on the road.
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"I’ve been told that it’s fairly flat today fingers crossed, they might just be lying to me."
She's joined by endurance challenge professional Greg Whyte, who was with Radio One DJ Greg James last week - with the pair forced to abandon their Three Peaks challenge due to the red weather warnings in Scotland.
Zoe added: "The fact that he’s come back has given me hope.
"We have clear blue skies here in Blackpool but I have been told there might be side wind."
She's completing the BT Sport Relief Challenge to raise awareness of mental health issues, following the death of her partner Billy Yates last May.
She was joined by Billy's sister Katherine McKee and best friend Beth Simpson on the starting line in front of Blackpool Tower.
Follow Zoe's journey and donate at sportrelief.com/zoe