$query="select Username from Users where Username like 'Ben'";
$result=mysql_query($query)
if(mysql_num_rows($result)>0) //<--NOTE
{ ...'Ben' is already in use ...
}
Of course, better is to get MySQL to do the counting...
$query="select count(username) as taken from Users where username like 'Ben'";
$result=mysql_query($query);
$taken=mysql_result($result,'taken');
...and $taken will be the number of Usernames in Users that are like 'Ben'.