Port 25 is the port used to send email via the Internet. Some Internet service providers (ISPs) block port 25 when you are outside the ISP's network, to reduce the amount of junk mail originating from their domain. By blocking port 25, the ISP forces its customers to use the outgoing (SMTP) mail server provided by the ISP, rather than the SMTP server on their computers, so the ISP can monitor the outgoing mail and track down junk mail senders.
Try the following:
Ask your ISP if they are blocking port 25 and if you can use any return address, or if you are required to use the address you have with them.
For .Mac accounts, if your ISP is blocking port 25 but not port 587, change the port to 587 and try again. Choose Mail > Preferences, and click Accounts. Select your .Mac account, then click Account Information. Click the Server Settings button and then replace 25 with 587 in the Server port field. Click OK and close the Preferences window. Try sending your message again.