你应该这样做：

$sql = "SELECT DISTINCT Branch FROM student_main";
$result = mysql_query($sql);

echo "<select name='Branch'>";
while ($row = mysql_fetch_array($result)) {
    echo "<option value='".$row[0]."'>".$row[0]."</option>";
}
echo "</select>";

echo "<input type='submit' Value='submit' />";
echo "</form>";