Humphries, from Calgary, and Valouis, from Wakaw, Sask., finished with a two-run time of one minute 56.53 seconds.
"We were close to pushing a start record for this track so it was a really good day for us," said Humphries, following her fourth national title. "There was lots of snow on the first run and then the track sped up."
The veteran was proud of her teammate.
"I know Chelsea was a little nervous," said Humphries. "This was the 15th and 16th time she has been down a bobsleigh track so it was great to see her do well. We have lots of work ahead of us but we are excited for the season."
Edmonton's Jenny Ciochetti teamed up with Calgary's Kate O'Brien to finish second at 1:57.87, while Calgary's Rosalyn Nykolichuk and Winnipeg's Chelsey Kaprenko locked up the bronze medal with a time of 2:00.45.
Meanwhile, Calgary's Chris Spring showed he is back on track after horrific crash in Germany last January that sidelined him for the remainder of the season by winning his first Canadian championship.
The 28-year-old Spring joined forces with Adam Rosencke to post a winning time of 1:53.94.
"This was the start I was planning for coming back to the sport after my injury," said Spring. "It was bittersweet with (No. 1 pilot Lyndon) Rush not in the race, but Justin Kripps and his team have been keeping me honest since Day 1 this year."
Spring likes the direction the sport is headed in Canada.
"I think the real winner today is Bobsleigh Canada," said Spring. "There are so many good athletes coming through the program and it makes me happy to see the camaraderie between all of the athletes."
Kripps and brakeman, Nick Carrier, grabbed the silver medal with a time of 1:54.58, while Hamilton's Chris Korol and Ben Klepacki slid into third place at 1:56.22.
Earlier Saturday, Canada's top skeleton athletes hit the track.
Three Calgarians grabbed the hardware in the women's race. Sarah Reid locked up her first national title with times of 59.20 and 59.92 seconds. Cassie Hawrysh was second (59.32/59.92), while Lanette Prediger placed third (59.16/1:00.89).
Eric Neilson, of Kelowna, B.C., slid to his second-straight national title in the men's race with times of 57.99 and 58.20. Dan Greszczyszyn slid to the silver medal after clocking times of 58.13 and 58.66. Calgary's John Fairbairn rounded out the podium in third (58.16/58.73).