Depends on the year and how much there is left over from the week of Pesach. Nightfall plus the hour or so until the chametz sold over the week comes back into Jewish hands would be the absolute earliest, but it usually takes at least two hours to get all the Pesach dishes and pots and stuff washed, out of the way, packed up, etc. before I could even think of having chametz. However, I'm not really into chametz, and I often finish up the left over matzah lasagna and other things for the next few days. Many years I don't have actual chametz until the challah on Friday night! (With a key in it!)
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