Charles Kennedy has said Met Police chief Sir Ian Blair "overstepped the mark" with his support for proposals to hold terrorist suspects for 90 days.
Mr Kennedy said Sir Ian should explain to a Commons committee
The Liberal Democrat leader will enter the row on BBC One's The Politics Show.
Defence Secretary John Reid has denied Tory claims police were "politicised" in the run-up to last week's vote.
Meanwhile, Michael Howard has written to Tony Blair asking if police need the minister's permission to appear in the media, following remarks by Mr Reid.
This week MPs voted against a proposal to allow police to detain terror suspects for up to 90 days without charge, but later backed extending the detention time limit to 28 days.
The Tories have called for an inquiry into alleged lobbying of MPs by chief constables in the days before the vote.
Mr Reid has said their accusations were a "smokescreen" to cover their embarrassment at blocking the proposals.
Home Secretary Charles Clarke has admitted writing to the Association of Chief Police Officers (Acpo), requesting senior officers be available to provide advice for MPs.
But in a letter to The Daily Telegraph on Saturday Mr Clarke denied claims that this had amounted to the "politicisation" of the police.
The Conservatives allege Acpo was put under pressure to back Tony Blair's campaign to secure the 90-day detention.
Mr Reid accused the opposition of a "slur on the integrity of the police".
In an interview for The Politics Show to be broadcast on Sunday, Mr Kennedy says he does not think it was "legitimate" for the police to take a "particular view in a particular way and put it out there in the political arena".
He said Sir Ian Blair should appear before a Commons Select Committee to explain what happened in the run-up to the vote.
"When the chief of the Metropolitan Police takes such a high profile, as he did, over a specific amendment to a piece of government legislation questions have to be asked, I think it's overstepping the mark".
He added that there was "a good case to be made" for saying the police had allowed themselves to get dragged too much into the parliamentary politics of the situation.
Meanwhile, Tory leader Michael Howard has asked the prime minister if police need authorisation from the home secretary before appearing in the media.
The letter came in response to remarks made by Mr Reid on BBC Radio 4's Today programme on Saturday, which appeared to suggest that every interview now needed specific approval.
But the Home Office has denied the suggestion, adding that the police remain "operationally independent" of the government.
On the same programme Mr Reid denied the police had been playing politics, saying they had only being providing their expert advice on public safety, something they had done for governments of all persuasions.
He added that Mr Clarke had not dictated what the officers should say, or put pressure on them, but asked them to stand ready to give advice if they were approached by their local MPs.
Conservatives Stephen Dorrell and Peter Lilley have tabled a parliamentary motion condemning ministers for "embroiling them in politics".
They say MPs received telephone calls, emails and letters from chief constables.
Former chief constable of Humberside, David Westwood, said a damaging perception had arisen that police were trying to influence the parliamentary process.
"I don't think there's anything wrong with inviting MPs to consult their chief constable. The problem in this instance was the closeness in time to the parliamentary vote."