Nearly 10,000 more A*s were awarded than expected in the first year of the elite grade, A-level results published last week show.
The news bears out heads' predictions that the new top rating would motivate the most able pupils to work harder as they approached the end of their A-level courses.
But, with as many 200,000 pupils expected to miss out on scarce university places, it will make the fight to win entry to institutions like Cambridge even tougher.
It came as the overall pass rate rose for the 28th year in a row with 97.6 per cent of all A-levels gaining at least an E grade. A grades were also up, for a 12th successive time, and awarded to 27 per cent of all A- levels.
Jim Sinclair, director of the Joint Council for Qualifications, said it was "a day for celebration". But his comments were unlikely to quell the annual claims of dumbing down and grade inflation.
Science, maths and technology (STEM) subjects continued their revival, with entries boosted in maths, further maths, biology, chemistry and physics. French and German were down again.
Of all grades issued to girls 8.3 per cent were A*, compared with 7.9 per cent for boys, confounding the expectations of some academics. But boys outperformed girls at A* overall within the STEM subjects.
In Wales, the A-level pass rate dropped for the first time since the qualification was reformed 10 years ago. The proportion gaining A*-E grades was 97.1 per cent, marginally below the figure in England.
Welsh A-level students also underperformed compared with their English counterparts in terms of the new A* grade, gained by only 6.5 per cent in the principality compared with 8.1 per cent over the border.
Gareth Pierce, chief executive of the WJEC exam board, said the results were still "very pleasing".
He added: "Given the influence of the independent school sector in England, where a comparatively larger proportion of A* grades was obtained than in the maintained sector, Wales's results compare very well."
Northern Ireland was once again the best performer in the rest of the UK, with 9.3 per cent of entries gaining the new top grade. But the pass rate dropped from 98.4 per cent to 98.1 per cent.
William Stewart firstname.lastname@example.org.