Just wanted to post, because after hours of struggling with the above error, I resorted to downgrading my PHP version to 5.2.17.
However, it was only the post above which eventually enabled me to work out how to get the new PHP module working with MySQL!
I had uncommented the extension and entered the file path as countless forums have specified, but the key information was here:
As AcidicChip states (back in 2006), the file libmysql.dll must be in the Apache bin directory for this to work.
And it does! Many thanks for that.