you could:
Run your query
Use the mysql_num_rows() function to see how many rows where returned.
If 0 were returned, safe to register it.
If more than 0 returned, username is already present in the database.
eg:
$query = "SELECT username FROM user WHERE username='$username'";
$result = mysql_query($query,$dbconnectionvar);
$isregistered = mysql_num_rows($result);
if ($isregistered != 0) { echo "Username taken!"; exit; } else {
// insert code and processing
echo "Username registered!"; }