Clackmannanshire results show the No vote at 54 per cent to 46 per cent for the Yes campaign, the BBC reports. In Orkney, the No side won roughly 67 per cent to 33 per cent.
The question on the ballot asked voters simply: "Should Scotland be an independent country?" and a record number of voters were expected to turn out for their chance to weigh in on the question.
Local officials said that more than 4.2 million people registered to cast a ballot in the referendum, which represents roughly 97 per cent of all eligible voters. Included in those eligible to vote were people as young as 16.
Results from the 32 local centres are expected to come in through the night, as councils tally up what's expected to be a record number of votes. Final results are expected sometime between 1 a.m. and 3 a.m. ET.
Alex Salmond, the first minister who led the independence campaign, made a final effort to woo voters Wednesday, saying the referendum represented an "opportunity of a lifetime."
British Prime Minister David Cameron made a case for a No vote days earlier, warning that a vote for independence would be "forever" and urging voters to choose to stick together.
CBC's Nahlah Ayed, reporting from Edinburgh, said there has been a "real sense of occasion" throughout the day as voters went to the polls.
Ayed noted that there was a great deal of excitement, but also a lot of nervousness as people wait for the official results.
Ross Paton, a farmer who has been part of the Yes campaign, told CBC's Rosemary Barton that he wants independence for Scotland for many reasons — some political, some personal.
Politically, he said, he wanted to see changes to the voting system and some land reform.
"On a more personal political level, I get fed up with the U.K. pretending to be a great power in the world and it actually makes me a bit embarrassed," he said.
He said he felt independence would help the whole U.K.
"It will create a disruption in the establishment, I think it will democratize the whole of the island at the end of the day."
British Conservative MP Andrew Percy, who was with the No campaign, said he thinks it will be close, but he's expecting voters will choose to stay with the U.K., despite some bumbling by the leaders of the No campaign.
The campaign to keep the U.K. together was too negative, he said, calling it a "complete disaster" that failed to connect with many voters in Scotland.
"I think party leaders at Westminster completely failed to wake up to what the nationalists were up to," he said. "Everybody has been stumbling about last minute trying to get promises out left, right and centre to the Scots to try and make them vote No."
He said the leaders failed to make the case for Scotland's place in the union.
Even if the No side is successful, he said, there will still be constitutional challenges because of all the devolution promises that were made.
"There's going to be a complete and utter constitutional mess that needs sorting out if Scotland votes No," he said, adding that a No vote doesn't mean a return to the status quo.
'Politics for everyone'
CBC's Margaret Evans said the Yes campaign has spent a great deal of time trying to win over voters in Scotland's low-income neighbourhoods.Sonia Black, a student campaigner, told Evans that many people she spoke to felt they were being heard for the first time with this vote.
"They feel like … the tide is turning and their opinions matter," she said from Edinburgh. "Their opinions are just as important as someone who has an economics degree from Cambridge, or whatever … It's supposed to be politics for everyone, not just for the few."
Fiona Mowat, a PhD student at the University of Edinburgh, said she was voting Yes despite some lingering questions about what might come along with independence.
"Often we tend to vote more liberally, more left wing," she said, adding that those votes were not well reflected in "who we're ultimately ruled by."
Scotland has a population of just over 5 million, a small proportion of the more than 64 million people in the broader U.K.
Alex Imrie, a fellow PhD student, felt differently and said he was voting No.
"I don't think the answer is to become parochial and inward looking in how we define our national borders that way — I think that's the wrong way to do it," he said. "The drive should be to improve the situation overall within the terms of the union."
A vote for independence would trigger 18 months of negotiations on how the two countries would separate their institutions before Scotland's planned Independence Day on March 24, 2016.