Five young people supported by projects funded by CiN will be pedaling around the clock along with their riding partners, including Alex.
Alex's co-host Matt Baker, who completed the challenge last year, will also be riding alongside the team to act as a mentor and provide team support.
The riders are set to pedal furiously throughout the UK, covering 700 miles to raise money for Children in Need.
The epic journey will begin on Friday 8 November in Northern Ireland, then the team will then cross the Irish Sea in to Scotland before heading to Wales and England.
The Rickshaw peddlers have so far raised a whopping £3.5 million for Children in Need in a mere three years.
Rickshaw veteran Matt said: "As a former rickshaw rider I know what lies ahead for the team, so the advice I'm giving them is a little sugar coated at the moment, otherwise they might not turn up!
"I only hope that the UK gets out on the streets as they have done in the past; it's this support that will get them to the finish line."
Co-presenter Alex added: "This is going to be one of the toughest things I've ever done, and we will all have our work cut out for us. Cycling through the night will probably be the hardest part."
The BBC Children in Need appeal will join the team live on air on Friday 15 November.
One Show viewers will be able to follow Team Rickshaw's progress each day, and updates will also be available online and on Twitter via #TeamRickshaw.
To support the challenge and donate £5, text TEAM to 70705. Texts cost £5 plus one standard rate message; £5 will go to BBC Children in Need. Head here for full terms and conditions. You must be over 16 and ask the bill payer's permission.