The grainy CCTV images show the pair an hour after being exposed to novichok in March 2018.
Mr Skripal, who touched the nerve agent that had been smeared on his door handle, can be seen holding his head as he comes out of a pub.
He and Yulia then go to Zizzi's restaurant before slumping on a park bench, in a poisoning that killed Dawn Sturgess, 44, in July that year.
As the inquiry into her death began yesterday, Mr Skripal said he believes Vladimir Putin was behind his attack.
Mum-of-three Dawn was killed by the nerve agent that had been left in a discarded perfume bottle, which contained "enough poison to kill thousands of people".
She was pictured in a dress and hat in Salisbury, Wilts, on the day before she died and also in June.
The Skripals were seen feeding ducks and giving bread to a boy, too.
Hauntingly, pictures show the Skripals could have driven past their alleged Russian assassins on the day they were poisoned. Footage shows the Skripals driving into town in their black BMW and a short time later Alexander Petrov and Ruslan Boshirov walking up the same road.
The father and daughter will not be appearing in person at the inquiry in Salisbury but in a statement Mr Skripal outlined how he was certain Putin was behind it.
He said: "I believe Putin makes all important decisions himself. I think he must have at least given permission for the attack on Yulia and me."
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