Welcome to Android Central! Which phone? Which email provider are you using? You may have to check the outgoing SMTP server settings and make sure they match your email provider's settings. Open the Email app, tap Menu>Settings, then select the email account. Look for an option for server settings, and look for the Outgoing SMTP Server Settings. Make sure they match your email provider's settings--you can find it by Googling "[your email provider] IMAP POP3 settings."
You can also try removing that email account, then adding it back again to see if it clears up the problem.