Steven Moffat's climactic episode, starring Matt Smith and Alex Kingston, averaged 6.09m (28.3%) for BBC One between 7.05pm and 7.50pm, up 840k on last week's 'Closing Time'.
'The Wedding of River Song', which saw the Time Lord survive Lake Silencio, represents Doctor Who's best overnight performance since 'Let's Kill Hitler' in August, which had 6.2m.
Doctor Who Confidential's final airing on BBC Three logged 397k (1.7%) following the announcement that the behind-the-scenes show would not return next year.
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After Doctor Who, Merlin captured 5.23m (22.7%) for its series four opener, down 400k year-on-year.
You've Been Framed (6pm) and All Star Family Fortunes (6.30pm) plunged to 1.87m (11%) and 3.48m (17.7%), adding respective ITV1 +1 audiences of 198k (1%) and 213k (0.9%).
Spinoff show The Xtra Factor then mustered 899k (4.5%) on ITV2 (+1: 196k, 1.3%), while The Jonathan Ross Show held 3.54m (17.6%) on ITV1 (+1: 388, 2.6%).
Meanwhile, The National Lottery: Secret Fortune picked up 3.75m (16.3%) for BBC One from 8.30pm. An instalment of Casualty titled 'Wild Horses' managed 4.4m (21.5%) an hour later.
Channel 4's screening of X Men Origins: Wolverine thrilled 659k (2.9%) from 7.30pm (+1: 250k, 1.2%). Davina McCall's Million Pound Drop followed with 1.47m (7.7%) at 9.30pm (+1: 171k, 1.3%).
Elsewhere, Big Brother dipped to 971k (4.8%) on Channel 5 at 9.30pm, while 5*'s Bit on the Side fetched 144k (1%). NCIS (8pm) and Law & Order: SVU (10pm) drew 595k (2.6%) and 750k (4.9%) either side of the revived reality show.
Overall, ITV1 stormed primetime with 30.5% (+1: 2.1%) against BBC One's 22.6%. Channel 4 claimed third place with 4.4% (+1: 0.9%), ahead of Channel 5's 3.8% and BBC Two's 3.6%.
High scorers on the digital channels included ITV2's 10.30pm Celebrity Juice catch-up which catered for 600k (3.8%), while BBC Three's movie Con Air brought in 658k (3.7%) from 9.30pm.
BARB ratings data supplied by Attentional