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The track, which achieved first week sales of 187,100, sold over double the amount of her nearest rival Robbie Williams, who debuted at two with 'Bodies'.
"I'm blown away. I've been recording my album for the last six months, so I'm hugely excited to finally be sharing my music with everyone," she told the BBC.
"I want to say a big thank you for all the support I'm receiving, I'm one very happy girl today."
HMV spokesperson Gennaro Castaldo claimed that Burke has a "tremendous platform" for success with her debut album Overcome, which is released today.
"Fending off the mighty challenge of Robbie on his return, shows that her fan base has not only stayed with her, but is growing as she connects with a wider audience," he said.
Burke first reached number one with her X Factor winning single 'Hallelujah' last December.
> Click here to watch our recent interview with Alexandra Burke
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