But Moeen, dropped on 15, thrashed 67 off 59 balls including three sixes - the second of which took him to fifty, launched onto the England balcony where it was caught by Jonny Bairstow.
England were bidding for a first home Test series win over SA since 1998, with Joe Root seeking a victory in his first Test series as England captain.
England had struggled against the spin of Keshav Maharaj who was making the most of the rough outside off-stump to the left-handed batsmen.
Moeen Ali is in the form of his life.
But just as the players were walking back on for the start of South Africa's second innings, rain lashed down on Old Trafford and stopped play before a ball had been bowled in the Proteas' chase.
Despite almost going first ball as the fourth of Duanne Olivier's victims in a decent spell from the James Anderson End, chopping past his leg stump on the first ball he faced and then being dropped, he has the attitude to make the most of his luck.
His 17 wickets in the series hardly do his work justice, and he set the tone for South Africa's initially excellent Sunday by removing both Alastair Cook and Westley in the morning session as he charged in to deliver pace and precision in equal measure.
It was also just South Africa's second defeat in 20 away Test series, their other overseas campaign reverse in that sequence coming against India in 2015/16. He had added just one to his interval score when he edged a cut off Kagiso Rabada to first slip Hashim Amla.
Jonny Bairstow earlier hit 99 as England rallied to 362 all out.
But the Middlesex left-hander, born in London but brought up in South Africa, exited for six - having been dropped on five - when caught via bat and pad at short leg off Maharaj.
With two full days still available, although the weather could be an issue, England are unlikely to declare any time soon as it is the Proteas who have to make the running to win the match and square the series.
This was turning into a fine spell by Olivier, whose two wickets for four runs in eight balls threatened to put the contest back in the balance.
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