It was knocked off the top of the league table by Winchester last year, but has now regained the position it has held since league tables started, three years ago.
Westminster, London, which charges pounds 12,750 a year for sixth-form boarders, beat St Paul's into second place with an average points score of 31 per candidate, based on 10 points for an A grade, down to two points for an E grade.
David Summerscale, the head teacher, put the success down to 'superb teaching and obviously able pupils who are able to respond to the pressures they have to face . . .
'I think above all there is a very good academic atmosphere which is part of the tradition of the school. So the teacher and the taught enjoy what they are doing.'
Westminster has 649 pupils, including 85 girls in the sixth form. It selects pupils at the age of 13, by common entrance and its own scholarship examination.
Before the Reformation, the Benedictine monks of Westminster Abbey had run a small school for boys. The monastery was dissolved in 1540 but Henry VIII ensured that the school carried on.
Westminster has a distinguished record and old boys include the Labour MP Tony Benn, the composer Sir Andrew Lloyd Webber, and Nigel Lawson, the former Chancellor of the Exchequer.
Mr Summerscale said he still had misgivings about league tables.
'They do not necessarily reflect the full quality of the school. They have also added to the pressure that we are all under, which I regret. But I think that there is now a better awareness of what league tables are, and what they are not,' he said.
But can state schools ever catch up with independent schools? 'That is obviously a serious and important question,' he said.
'There is excellent work being done in the sixth forms in the maintained sector. People who stay on to the sixth form do so because they want to study. Once it becomes obvious that this will lead to a good place at university and a good career afterwards, more people will stay on and it will be easier for excellent teaching to develop . . . I hope then that the huge gap between independent and state schools will decrease.'
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