The SNP leader visited Annette Street Primary School in Govanhill – part of her Glasgow Southside constituency – along with Roza Salih, who is the lead SNP candidate on the Glasgow regional list.
Ms Salih will become the first former refugee to be elected to Holyrood if she wins a seat, with this year’s poll being the first in which people with refugee status are entitled to vote.
At the polling station, Ms Sturgeon and Ms Salih met three Syrian Scots who have lived in Scotland for eight years – 63-year-old Adnan Abdulbaki, and Iqbal Abdulbaki and Abdulruhman Abdulbaki, both 20 – as they prepared to cast their vote.
Ms Sturgeon said it is “great we’ve got everybody who lives here able to vote”, saying it is an “exciting” and “special thing to do”, to which they agreed.
She expressed hope that Ms Salih will be an SNP MSP once the votes are counted this weekend.
Despite alluding to the fact she is scared of dogs, Ms Sturgeon also had her photo taken with a pet called Elsa outside the school.
An interpreter for the Syrian Scots requested a selfie with the First Minister and said his mother is unwell with Covid-19, so asked if she could record a video message for her.
Ms Sturgeon did so, and in the message she said: “It’s Nicola Sturgeon here, First Minister of Scotland, with your son in Glasgow.
“I understand you’re not well with Covid so I wanted to send you my best wishes for a speedy recovery. Get well soon.”
A man wearing an SNP rosette outside the polling station, alongside a young boy waving an SNP flag, told Ms Sturgeon they will be spending the day “campaigning for Auntie Nicola”.
The boy suggested he could take a photo with the party photographer in it, to which Ms Sturgeon said: “If it makes you feel any better it’s usually my job he’s after.”
Meanwhile, Scottish Labour leader Anas Sarwar voted at his local polling station at Pollokshields Burgh Hall in Glasgow on Thursday morning.
Mr Sarwar is standing against First Minister Nicola Sturgeon in the Glasgow Southside constituency, which includes Pollokshields.
Flanked by his wife and four-year-old son, Mr Sarwar was in a buoyant mood, chatting with voters and answering questions from journalists.
He said he used both votes for Scottish Labour and urged other voters to do the same.
Scottish Greens co-leader Lorna Slater will vote at a primary school in Edinburgh, while her fellow co-leader Patrick Harvie will vote at a school in Glasgow.
Scottish Conservative leader Douglas Ross will vote in Moray, while Alba Party leader Alex Salmond cast his ballot in Strichen, Aberdeenshire.
Scottish Liberal Democrat leader Willie Rennie has already voted by post.