The Xtra Factor host starts at number one with his new single 'Troublemaker' on this week's chart.
Murs is currently 28,000 copies ahead of Girls Aloud's comeback single 'Something New' at two, which has also been released to raise money for Children in Need.
One Direction slip to three with 'Little Things', Alicia Keys is at four with 'Girl On Fire' and Labrinth's 'Beneath Your Beautiful' is at five.
Rudimental land at 11 with new cut 'Not Giving In', while Ludacris clocks in at 39 with Usher and David Guetta hook-up 'Rest Of My Life'.
Over on the album chart, Rihanna has stormed straight to the top with her seventh studio collection Unapologetic.
Little Mix's debut album DNA starts at four and is trailed by Susan Boyle's Standing Ovation at five.
Elsewhere, Example is at seven with The Evolution of Man, AC/DC are at 14 with Live at the River Plate and I Will Always Love You - The Best of Whitney Houston is at 29.
Watch the music video for Olly Murs's 'Troublemaker' below: