You will need to make sure Apache is compiled with mod_userdir. Check the httpd.conf and search for mod_userdir. There should be a AddModule and LoadModule for mod_userdir.
Then check the section
Quote:
# UserDir: The name of the directory which is appended onto a user's home
# directory if a ~user request is received.
#
<IfModule mod_userdir.c>
UserDir public_html
</IfModule>
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Restart Apache if any changes have been made. You should then be able to access the user's home directory via
http://domain.com/~username/