On a hot, still evening in the Olympic Stadium where Usain Bolt set the world record of 9.58 seconds, Hughes, an occasional training partner of the great Jamaican back in Kingston, set a Championship record of 9.95 to pip fast-finishing team mate Reece Prescod by one-hundredth of a second.
The race to find the continent's fastest woman saw Asher-Smith end the 100m reign of Dutchwoman Daphne Schippers in brilliant style, clocking 10.85, equalling the world's fastest time this year and setting a British record.
The 22-year-old Asher-Smith, the reigning European 200m champion, surged clear early in the race, with Germany's Gina Lueckenkemper taking silver in 10.98 and Schippers bronze in a season's best 10.99.
It is the first time Britain have been able to boast both the men's and women's champion at the same edition in the 84-year history of the Championships.
The country's sprint domination on the opening day of finals was underlined by Britain boasting three men in the top four, with Chijindu 'CJ' Ujah clocking 10.06 behind Turkish bronze medallist Jak Ali Harvey (10.01).
The result, though, may have been different had France's Jimmy Vicaud, the fastest qualifier with an effortless 9.97 semi, not pulled out before the final with an adductor injury.
"I am happy and the job is done. I felt a bit of cramp so I don't think I could have gone any faster but I'm just happy," said Hughes, who was almost overhauled by Prescod as the silver medallist dipped under 10 seconds for the first time.
The 23-year-old Hughes was born and raised in the British Overseas Territory of Anguilla but has competed internationally for Britain for the past three years.
He has made rapid strides under Bolt's former coach Glen Mills but was left heartbroken in the Commonwealth Games when he was celebrating his 200m victory only to be told he had been disqualified for obstructing Trinidad's Jereem Richards.
As for any comparisons with his illustrious friend, Hughes just shrugged: "Usain Bolt did what he did at this stadium. I did the championships record and I am happy for that."
A beaming Asher-Smith, who looks set to be one of athletics' new shining personalities, said after her win: "I'm really really happy, I knew I had it in my legs. I did everything right.
"In the heats, I sat in the blocks like I was a slug and my reaction time was 0.2 (of a second) and I was like, 'what you doing, Dina, you're here to run. I was really happy to nail it in the final."
On the first night of finals, 30-year-old Frenchman Morhad Amdouni won a tactical 10,000m, sprinting away from Bashir Abdi after the Belgian tried to kick for home off the back straight and winning in a modest 28 minutes 11.22.
Earlier, Ukrainian Maryan Zakalnytskyy and Portugal's Ines Henriques were the first two champions crowned when they delivered exceptional 50-km race walk triumphs around the streets of Berlin on a hot morning.
French world champion Kevin Mayer, hot favourite to win the decathlon title, blew his chances completely in the second of the 10 events when he fouled in all three long jump attempts.
The Olympic silver medallist was leading the competition to find Europe's top all-round athlete after a 10.64 seconds run in the 100 metres before he made the inexplicable error which ruled him out of contention and prompted him to pull out.
Having fouled his first two jumps in the Olympic Stadium, just a safe third would have sufficed for the 26-year-old but he again edged over the take-off board with an unnecessarily aggressive approach on his final attempt.
Mayer's absence leaves the title up for grabs, with Britain's Tim Duckworth taking most advantage to lead by 95 points on 4,380 after the first day.
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