Backed by the Njernda Aboriginal Corporation, the young people will paddle eight kayaks from Yarrawonga to Koondrook during the five-day event.
They will also be joined by NSW police officers, teachers and government department representatives, who will help paddle and support them along the way.
Team co-ordinator Keisha Egan said the program was a chance for the participants to bridge relationships with key community figures.
“It's just an opportunity for the communities that live in those border communities to come together and work together with the police community and also the education department,” she said.
“The goal for this program is around cultural outcomes as well as outcomes for them to sort of bridge that gap between police and youth, to try and minimise youth incarceration.”
The five-day event will see all competitors travel a total of 415km along the Murray River, stopping along the way to rest.
The young paddlers were up early on Monday to get ready and eat breakfast at 4.30am before setting off at 5am to the start site in Yarrawonga.
At 7am they were in the water, aiming to cover 89km before wrapping up in Tocumwal for the first day.
From Tocumwal, the group will head to Picnic Point on day two and from Picnic Point to Moama on Wednesday.
Vessels will then set off again on day four from Moama Beach on Thursday morning as they head on to Torrumbarry.
Following a final 95km paddle, the event will wrap up in Koondrook on Friday, November 21.
Mrs Egan said the group had been in high spirits during the first day of the event.
“When they get off the boat, they’re just super proud of themselves,” she said.
“They’re extremely sore but so happy with their achievements because they’ve done such a massive thing.
“They push themselves beyond their own beliefs, and they've got that support of the paddler in the back ... (a) community worker, police officer or teacher that helps support them and get them to that finish line.”
Competitors are encouraged to raise money for a cause of their choice, with the event generating $1.1 million since 2016.