We are slowly PTing DD - basically offer the potty every hour or so, encourage her to tell us if she needs to go, etc., etc.
I want to encourage her to use the potty when she first wakes up in the morning but at least 50% of the time she wakes up crying and upset (and still half asleep) and asks to eat immediately. I normally take her downstairs and give her some cereal while she's in her PJs and I have my breakfast too. She's normally sleepy but wakes up while she's eating.
I feel like she should use the potty RIGHT when she gets up, but if I told/asked her to use the potty when she got up, she'd probably just get upset b/c she's so tired and out of it. But, if I wait until she's more awake, I think it'll turn into a game and she'll spend 20 minutes messing around in there when I actually need her (and me) to get dressed so we can leave.