Williams released his much anticipated dance/electro album, Rudebox, on 23 October 2006. It featured collaborations with the Pet Shop Boys, William Orbit, Soul Mekanik, Joey Negro, Mark Ronson, Chris Grierson, and The Orr Boys. It received mixed reviews: Allmusic gave it a four star rating, the NME 8 out of 10, and Music Week and MOJO were equally positive, but it received much weaker reviews from some of the British press. The album sold 2x Platinum in Europe with sales of over 2 million making it the fastest platinum-selling album of 2006. To promote his album, Williams commissioned a series of short films. Goodbye to the Normals was directed by Jim Field Smith and features "Burslem Normals" by Williams.
Since 2006, Williams has spent most of his time in Los Angeles. He briefly moved back to the UK in 2009 when he bought an £8.5 million mansion in Compton Bassett, Wiltshire, but sold the property a year later to move back to Los Angeles. In 2017 he sold his mansion in Beverly Hills for $9.9 million to DJ Khaled. In 2016 he moved into a £17 million mansion in Kensington, West London. His next door neighbour in London is Led Zeppelin guitarist Jimmy Page. In a long-running planning battle between the two musicians, Page delayed Williams' plans for an underground swimming pool in 2018, stating construction work would damage The Tower House, Page's home since 1972: a listed Victorian era townhouse described by the architectural historian J. Mordaunt Crook as "the most complete example of a medieval secular interior produced by the Gothic Revival, and the last".
In May 2006, Williams started dating the American actress Ayda Field. She was featured in the UFO documentary that Williams did for BBC Radio 4 , and took part in a field investigation he did in Trout Lake, Washington in 2008. Williams and Field wed at his home in Mulholland Estates in Beverly Hills on 7 August 2010. They have four children: a daughter, Theodora, (b.2012), a son, Charlton, (b.2014), a daughter, Colette, (b.2018), and a son, Beau, (b.2020).
Williams, with the help of friend Jonathan Wilkes, has organised charity football matches called Soccer Aid to raise money for UNICEF UK. A mixture of celebrities and professional football players have played Soccer Aid matches in 2006, 2008, 2010, 2012, 2014, 2016 and 2018 at Old Trafford in Manchester and Wembley Stadium in London.