Suppose you change LIMIT 1 to 5, I believe it's adding to the array, so you'd also need to add the extra values in echo"", since it's only displaying the first element in the arrays.
Code:
$res = mysql_query("SELECT CharName FROM characters ORDER BY Level DESC LIMIT 5;");
$res2 = mysql_query("SELECT Level FROM characters ORDER BY Money DESC LIMIT 5;");
$val = mysql_fetch_array($res);
$val2 = mysql_fetch_array($res2);
echo "<div style='top: 200; left: 550; position: absolute; z-index: 1; visibility: show;'>Top Level<br> <b>Name:</b> ".$val[0]." - <b>Level:</b> ".$val2[0]." <b>Name:</b> ".$val[1]." - <b>Level:</b> ".$val2[1]." <b>Name:</b> ".$val[2]." - <b>Level:</b> ".$val2[2]." <b>Name:</b> ".$val[3]." - <b>Level:</b> ".$val2[3]." <b>Name:</b> ".$val[4]." - <b>Level:</b> ".$val2[4]."</div>";
Try that and see if it works.