The First Minister and SNP leader arrived at her local polling station in Glasgow at 8am on Thursday, accompanied by her husband Peter Murrell - who is the party’s chief executive.
The SNP is hoping to oust Labour from power in Glasgow City Council - Scotland’s largest local authority - where their rivals have been in charge since the authority was set up more than 20 years ago.
After winning overall control of two of Scotland’s 32 local authorities in 2012, the nationalists are also seeking to increase the number of town halls which are under their command.
The Tories, Liberal Democrats and Greens - who are fielding a record number of candidates in Scotland - are also hoping to make gains.
Meanwhile polls have warned that Labour, which won a majority in four councils five years ago, could be facing “heavy losses”.
• READ MORE: single transferable voting system (STV)
The vote will determine which political parties can form council administrations either by securing majority or minority control, or by agreeing coalition deals.
The local government election takes place just five weeks before the General Election, and follows campaigning across the country by political leaders.
While the election will provide an indication of support ahead of the Westminster poll, politicians from all parties stressed the important role councils play in areas such as education and social care, and have urged Scots to use their vote.
Under the single transferable vote (STV) system, voters are asked to rank the candidates in order of preference, with three or four councillors being elected to serve any one ward.
Votes will be tallied at count centres across Scotland on Friday, with results expected from around lunchtime onwards.
Ms Sturgeon said earlier that a vote for the SNP will protect local services.
The First Minister added: “At the polling station today, people need to vote SNP to stop Tory cuts, protect our public services and invest in our communities.
“An SNP vote is the only way to guarantee more affordable housing, a transformation in early learning and childcare, investing in our schools, more money and power for local communities and increased support for small businesses.
“Our council candidates will work hard to serve their constituencies, to make Scotland’s communities stronger, safer and more successful places to live and work in.”
Meanwhile the Scottish Conservatives will aim to build on their success at last year’s Holyrood elections, which saw leader Ruth Davidson win a constituency seat in the capital.
The Tories, who returned one councillor in Glasgow in 2012, will also hope to boost their numbers there after returning two regional MSPs for the city in the 2016 Holyrood election.
Scottish Labour leader Kezia Dugdale urged voters to back a “local champion” at the ballot box.
She said: “Today, voters can send the SNP a message that they do not want another divisive independence referendum.
“They have the chance to tell Nicola Sturgeon and Ruth Davidson that cutting local services to the bone is not just wrong - it is unacceptable.
“With Scottish Labour, people have the chance to elect a local champion who will stand up for communities and say no to a divisive second independence referendum.”
Ms Davidson cast her vote at the Cafe Camino polling station next to Edinburgh’s St Mary’s Cathedral at 10.30am.
The Scottish Conservative leader said she was “nervous” about the outcome of the vote.
“I always get really nervous at elections but our people have been working hard, so I hope very much that everyone comes out to vote. Obviously I hope very much that they vote Conservative but we’ll find out tomorrow,” she said.