Misty Cook was found in possession of a gun, which is prohibited as she is a convicted felon. There is no suggestion she was involved in Sunday's attack.
The 31-year-old nursing student's relationship with the gunman, Wade Michael Page, 40, ended this year.
Hundreds of people held a vigil for the victims in Oak Creek on Tuesday night.
Officials are due to hold a news conference on the shooting at 11:00 local time (16:00 GMT).
Cook, who was found to have a firearm at her Milwaukee home, has a previous conviction for fleeing and eluding a traffic officer, US media report.
"In a joint investigation with the FBI, the South Milwaukee Police Department has arrested Misty Cook on the crime of felon in possession of a firearm," said a statement from the Milwaukee police department.
"Charges will be sought through the Milwaukee County District Attorney's Office."
Correspondents say Cook may be able to help authorities get a better picture of Page's life in the weeks leading up to the shooting.
She declined to comment on the attack in an email to the Milwaukee Journal Sentinel newspaper.
"If I could say something to ease the pain of the victims and their families I would gladly do so. Unfortunately words do not begin to heal the pain they are going through," Cook wrote.
Temple member Karan Singh Toor said he felt proud to be an American when he saw people of different races attending Tuesday night's vigil.
"It makes me so happy to see how we all come together for peace," he told the Associated Press news agency.
The dead were five men and one woman, who ranged in age from 39 to 84.
Three others injured in the attack remained in critical condition on Tuesday, said hospital officials.
Page, who was shot dead by police in his gun attack, reportedly had ties to white supremacist groups and played in white power bands.
Officials say they may never fully understand what motivated the former US Army veteran from Colorado to launch the gun rampage.
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