They will also be supporting one of their personal assistants, Emily Clark, in her fundraising efforts.
Emily has bipolar disorder and is aiming to cycle the distance from Lands End to John O'Groats on a static bike at the county's police HQ in Devizes on Monday morning.
The 26-year-old is doing this from 9am to 5pm every weekday next week to raise awareness of mental health, and raise money for the Mental Health Foundation.
Emily, who also volunteers as a Special Constable, will be joined by colleagues on a second static bike who will help clock up the mileage toward her goal.
Emily said: "When I tell people I have bipolar they are often surprised because I have a full-time job, go to the gym and live a normal life and it's not what people expect.
"I want mental health issues to be out in the open, for people to be aware, to discuss it and so break the taboo which still exists."
She is one of Wiltshire Police's Blue Light Champions, one of over 20 volunteer staff members who help support other members of staff suffering with a mental health issue.
They can also offer on-going help, like encouraging someone to share a problem, and talk about it, and give them tips about coping strategies.
She added: "It’s not counselling, but when you’re having a tough time it can really help to talk things through with someone who’s maybe been through the same as you and who can guide you to other support services that may be able to help. "
The Chief Constable and Commissioner signed the Blue Light Time to Change Pledge in 2016 to support mental health in the workplace and challenge any discrimination or stigma that surrounds it.