Their track 'Bom Bom' has knocked Rita Ora's 'How We Do (Party)' off the top spot on the midweek chart.
Devlin currently sits at number five with his Ed Sheeran collaboration 'Watchtower', while Taylor Swift is at six with 'We Are Never Ever Getting Back Together'. Muse's 'Madness' has entered the chart at number 33.
On the album front, Emeli Sandé looks set to remain at number one, but faces stiff competition from Bloc Party.
Our Version of Events is just 200 copies ahead of Four, according to the Official Chart Update.
Sandé is now just 17,000 copies away from overtaking Adele to have the biggest-selling album of 2012.
Jessie Ware's debut album Devotion is at number five, while Trey Songz's fifth studio album Chapter V lands at six.
Watch Sam & The Womp's video for 'Bom Bom' below: