The 32-year-old R&B singer was joined by her husband Swizz Beatz at the Blackberry Secret Sessions held at Trinity Buoy Wharf E14 on Friday night.
Welcoming her to the show was Jonathan Ross, who in typical talk show fashion chatted away to them outside the venue.
Welcome! Jonathan Ross greets Alicia Keys and husband Swizz Beatz ahead of her Blackberry Secret Session show
Ross, 52, has interviewed Alicia three times already both during his time on BBC 1 and ITV.
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It is unlikely the talk show host had met Swizz, 34, before, but ever the jolly gentleman, the Camden-born TV star quickly shook his hand and welcomed him to the show.
Jonathan kept them there for a few minutes to catch up with them before he introduced Alicia to the waiting audience.
Golden boy: Jonathan Ross introduces himself to Alicia and Swizz outside the venue
Soother: Alicia carried a stainless steel thermos, that could have been filled with honey and lemon to keep her voice fresh
Double effort: Alicia had performed at the O2 arena only hours earlier on Friday night
Keys was carrying a stainless steel flask, which may well have been filled with lemon and honey to soothe her throat before her second performance of the night.
And she had arrived with Swizz in synchronised style.
Both music artists wore monochrome jackets with black tops and jeans, but while Alicia added colour through her red lip and nail design, her rapper husband incorporated green and blue into his outfit through his hat and trainers.
Holding hands, the couple walked up to the venue ready for the show at 11.45pm.
Co-ordinated: Both Swizz and his wife wore black and white jackets on the night
Introduction: Jonathan invited the Fallin' singer onto the stage and chatted to her before she performed
Giggle: True to form, Ross had Keys laughing during his introduction
At the O2, the Empire State Of Mind singer benefited from the support of Miguel and guest appearances from Labrinth and John Legend.
The former joined Alicia on stage to sing Express Yourself followed by Earthquake while Legend and Keys sang his song Ordinary People.
And just like the headliner, Miguel also played a second performance on Friday night for LoveDough at Proud Camden.
For everyone: The intimate gig was streamed live online at 11.45pm
Stripped back: Alicia performed some of her greatest hits and thanked Miguel, John Legend and Labrinth for their O2 support after the show
But Alicia's performance was streamed live online by Blackberry, allowing the world to witness the intimate gig from the comfort of their own home.
And the singer treated those in the audience, and on the web, to a stripped back selection of her favourite tracks.
Before she sang, Jonathan flirted outrageously with Alicia who also quizzed him on the British food, Jellied Eels.
Epic: Alicia performed at the O2 Arena earlier in the night
Duet: Labrinth joined Alicia on stage to sing Express Yourself followed by Earthquake