Brown was elected to the Scottish Parliament by Ochil constituency at the 2007 elections, increasing both absolute SNP vote and majority. He was appointed to be Convener of both the Parliament's Standards & Public Appointments Committee and Procedures Committee, and after overseeing their merger now convenes the new Standards, Procedures & Public Appointments Committee. In his maiden speech on the abolition of bridge tolls he declared that he still had an outstanding fine from the Skye Bridge protests of 1994. He has been an opponent of the proposals for an overhead electricity line from Beauly to Denny, arguing for an underground alternative. Brown has also been campaigning for Scotland football matches to be available on terrestrial television. On 12 February 2009, Brown was appointed Minister for Schools and Skills. On 8 December 2009, Brown became Minister for Schools and Skills In the first reshuffle of the SNP Government. In December 2010, he was appointed as Minister for Transport and Infrastructure in the Scottish government. Brown won re-election to the Scottish Parliament in 2011, representing the newly created Clackmannanshire and Dunblane. On 19 May 2011, Brown was named as the Minister for Housing and Transport. On 5 September 2012, he became Minister for Transport and Veterans.
On 21 November 2014, he was promoted to Cabinet Secretary for Infrastructure, Investment and Cities in Nicola Sturgeon's first reshuffle. Brown was re-elected to the Clackmannanshire and Dunblane constituency in 2016. On 18 May he became the Cabinet Secretary for the Economy, Jobs and Fair Work while still maintaining responsibility for veterans affairs. In December 2016, Brown led calls for Amazon to pay its employees the living wage after reports surfaced concerning the conditions of workers in the company's Dunfernline depot, holding talks with Amazon several days later in which he was told Amazon would "consider" paying the living wage. In July 2017, Brown wrote to UK ministers on the need to continue legal protected status for the definition of Scotch whisky post-Brexit amid fears that in a future trade deal the USA “would support a relaxation of the definition of whisky, which would open the market up to a number of products which do not currently meet that standard.” Later on in 2017 he visited the US and Canada in a series of speaking engagements to promote economic ties between North American business communities and Scotland.
Depute leader of the Scottish National Party
On 8 June 2018, Keith Brown became the depute leader of the Scottish National Party, having contested and won the 2018 Scottish National Party depute leadership election with 55% of votes in the second round. At his acceptance speech at the SNP conference in Aberdeen, Brown told fellow SNP members to prepare for a second Scottish independence referendum. Brown also announced that he would chair three national assemblies to debate the SNP's 2018 Growth Commission report on an independent Scotland's economic prospects. Although Brown was elected Depute Leader of the SNP, John Swinney remained as Sturgeon's Deputy First Minister despite Brown being a member of the Scottish Parliament. In the June 2018 reshuffle of the Scottish Government, Brown stood down as Economy Secretary to focus on his role as depute leader, He was replaced by Derek Mackay. He was subsequently given a role as the SNP's Campaign Manager.