The 'Gimme All Your Luvin' singer has now overtaken Elvis Presley's record of number one albums in the UK.
MDNA beat David Guetta's Nothing But the Beat by 34,000 copies, with Guetta remaining in the runner-up spot for a second week.
Emeli Sandé climbs a place to third position with Our Version of Events, while Adele continues her long-running success, with 21 rising to four.
Jessie J completes the top five, with Who You Are climbing 18 places to fifth position following her Voice UK debut last weekend.
Paul Weller tumbles from last week's number one spot to ten with Sonik Kicks, while Katy Perry climbs a whopping 28 places to six with Teenage Dream.
Rihanna also sees a big climb of 17 places to this week's 12 with Talk That Talk.
Tenor Noah Stewart scored this week's highest new entry at 14 with debut album Noah, while Shinedown achieved their first UK album placing with Amaryllis at 18.
Iron Maiden's latest live offering En Vivo lands at 19, with Alter Bridge's Live At Wembley collection entering the chart at 31.
The All-American Rejects complete this week's new entries with their latest album Kids in the Street at 34.
Source: Official Charts Company
> This week's singles chart
Watch the video for Madonna's 'Gimme All Your Luvin' below:
View the latest Official Top 100 Album Chart