According to reports, officers arrested Jerry Westrom last week after a genealogy firm analysed the sample and linked the businessman to the stabbing of 35-year-old Jeanne Ann 'Jeanie' Childs, back in 1993.
The 52-year-old from Isanti, Minnesota has reportedly denied all charges and has been released on a $1 million (£773,000) bail.
Childs' body was found by a neighbour who had noticed water coming from her apartment.
When police arrived at the scene, Childs, who had previously worked as a sex worker, was lying on the floor and had suffered a number of stab wounds.
Officers took DNA samples from a bed comforter, a towel in the bathroom and a washcloth from her toilet set.
Cold case investigators from Minneapolis Police Department and the FBI began a review of the case back in 2015, working alongside the Bureau of Criminal Apprehension Forensic Laboratory.
Three years later they then consulted with FBI experts and a private DNA company which revealed two possible suspects.
According to the Minneapolis State Tribune, one of them was Westrom, who lived close by at the time of the murder, and in 2016 had been charged with soliciting a teenager for sex.
Last month police followed him to a hockey match, where after watching him wipe his mouth and throw his napkin in the bin, they rifled through its contents until they found his tissue.
The father-of-three was then arrested at his office last Monday.
Minneapolis Police Chief Medaria Arradondo said: "Our efforts to increase public safety and ensure justice have no timeline. This case is an excellent example of great collaboration between our law enforcement partners."
Jill Sanborn, special agent in Charge of the Minneapolis Division of the FBI, added: "We all hope Jeanne's family can finally find peace as a result of this tenacious effort by officers and agents.
"This case underscores law enforcement's ability to use every tool at its disposal to crack a case .
"The BCA Forensic Science Services is committed to helping investigators understand the facts of an incident. We are continually working with our partners to bring answers to victims of crime no matter when the crime happened."
Hennepin County attorney Mike Freeman told press the arrest was the result of 'good police work.
He said: "This was a cold hit case. DNA samples were sent to genealogists who helped us match them together. This was good police work to pass this kind of technique on between cops."
Featured Image Credit: PA
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