The best and the only way to do so is given below. Just follow the steps as give and you’ll be using your Gmail account on Outlook Express in no time. :)

• Make sure POP access is turned on for your Gmail account.
• Select Tools | Accounts… from the menu in Outlook Express.
• Click Add | Mail….
• Type your name.
• Click Next >.
• Enter your Gmail address.
• Click Next >.
• Make sure POP3 is selected under My incoming mail server is a __ server..
• Type “pop.gmail.com” under Incoming mail (POP3, IMAP or HTTP) server:.
• Enter “smtp.gmail.com” under Outgoing mail (SMTP) server:.
• Click Next >.
• Type your full Gmail address under Account name:.
• Enter your Gmail password under Password:.
• Click Next >.
• Click Finish.
• Highlight the newly created pop.gmail.com account.
• Click Properties.
• Go to the Servers tab.
• Make sure My server requires authentication is checked under Outgoing Mail Server.
• Go to the Advanced tab.
• Make sure This server requires a secure connection (SSL) is checked under both Outgoing mail (SMTP): and Incoming mail (POP3):.
• Type “465″ under Outgoing server (SMTP):.
  • If the number under Incoming server (POP3): has not been changed to “995″ automatically, enter “995″ there.
• Click OK.
• Click Close.