Ontario Provincial Police said David James Leblanc, 47, was arrested Sunday evening when officers responded to reports of a man in distress near Longlac, about 260 kilometres northeast of Thunder Bay.
Stephane Garon was returning from a camping trip with his wife, when they spotted a man walking barefoot on the trail.
Garon said when he stopped to see if the man needed help, he noticed his face was full of scratches and he was disheveled
"We asked, 'Where are you from? Where's your truck? What happened?' And he kept saying he didn't know. So we gave him a bit of water, I was going to help him out because I didn't know who he was. My wife said, 'No, no, no. 'We'll get cell range and we'll call the police,'" said Garon.
He said they met police where the logging road meets the highway and told them where to go.
It wasn't until this morning when they saw news reports that he realized the man was wanted in Nova Scotia for forcible confinement and sexual assault.
Police say Leblanc will make an appearance Monday at a Thunder Bay court via video from the Greenstone OPP detachment. It will be up to RCMP in Nova Scotia to determine when Leblanc will be transported to that province.
"He was just wandering along the road. He appeared to be somewhat distressed from the elements. He wasn't dressed to be out in the kind of temperatures we have this time of year," said Staff Sgt. Carl Pettigrew.
Garon said there was no sign of Leblanc's co-accused and longtime partner Wayne Alan Cunningham, 31, or the 2003 Hyundai they were supposed to be driving.
Police believe Cunningham is still operating a grey-colored 2003 Hyundai Elantra with Nova Scotia licence plate FBP-233, and that he could be headed to Calgary.
A woman who knows Cunningham told CBC News the police should be on alert because he often passes himself off as a female. Anna Leblanc said Cunningham is very convincing as a woman and is known for telling people he's 19 or 20 years old.
Leblanc's relatives said they're glad he was arrested.
Jessica Clattenburg, Leblanc's niece, told CBC News her uncle stopped by the family house in Liverpool, N.S., last week to ask for $20 for gas.
"We would've thought that he would've just stayed local.… I don't know how he would've gotten the money to get that far," she said.
"I'm just glad that they caught him."
Teen in chains walked for help
Police say the two men held a 16-year-old boy in a Nova Scotia home for about two weeks in Upper Chelsea, Lunenburg County.
The teen escaped from the house and walked more than one kilometre to another home to ask for help.
The teen had chains wrapped around his wrists and ankles and was wearing nothing but a hooded sweatshirt and a hat when he arrived on Terry Frauzel's doorstep.
Frauzel told CBC News he cut the chains off the boy and drove him to a house in Bridgewater. The teen was later treated in hospital and police say he is now safe.
The search for Leblanc and Cunningham began after the two men were charged on Sept. 26.
Last week, the family of Leblanc issued a public plea for the suspect to turn himself in.
According to relatives of Leblanc, he and Cunningham have been in a common-law relationship for more than a decade.
Leblanc also faces charges from a separate case of making and distributing child pornography. He's also charged with sexual assault and sexual interference involving two young boys.
Cunningham also has a criminal record. He was convicted of several crimes including theft and breaking and entering after a 2006 incident in which Leblanc was also convicted.