The election of the First Minister, due to be held in Holyrood on Tuesday, is traditionally won by the leader of the largest party in the parliament.
The SNP was returned as the party of government with 64 seats in the parliamentary elections earlier this month.
The Scottish Liberal Democrats saw their representation reduced from five MSPs to four – which sees the party lose "main party status” within Holyrood, including the automatic right of the party’s leader to put a question at First Minister’s Questions.
While Ms Sturgeon will be elected as First Minister once again, Mr Rennie has said the event “should not just be an SNP cakewalk”.
He also stood against Ms Sturgeon for the position in 2016 when she was re-elected to the post by 63 votes to five, after the Conservatives, Labour and Greens abstained during the formal election contest, and the Lib Dems voting for their leader.
Mr Rennie said he would put himself forward on a platform of putting recovery first.
“In a parliament of minorities, it is important that there is a challenge,” he said.
"This should not just be an SNP cakewalk.
“Nicola Sturgeon and Douglas Ross are both obstacles on the path to tackling the issues that really matter. They both want to spend the next five years arguing over independence.
“As First Minister I would focus on education, mental health, jobs and the climate emergency. That’s a positive plan for Scotland. That’s how we put recovery first.”
MSPs are due to elect the First Minister at 2pm on Tuesday.
Under the Scotland Act 1998, a new First Minister must be elected within the first 28 days of the Holyrood election, or another Scottish election must be held. Each nominee is able to speak for five minutes in support of their candidacy before the voting process begins.
It is expected that Thursday will also see the appointment of government ministers.
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