i seem to have a problem with Mail.app on Lion. I have three accounts: two of them are gmail accounts and one is an exchange account. I've checked the 'Send new messages from account of selected mailbox' option in Preferences --> Composing. However, whenever i try to send mail from the first account it's send from the third account. I have no problems with the 2nd and 3rd accounts that do honour the correct sender.
This worked fine under Snow Leopard.
Solved now: i don't know what i did exactly but i fiddled around with some settings, disabled and enabled a few accounts and now suddenly Mail sends from the selected account again. Weird.