Handle error for duplicate entries - PHP MySQL

To check for this specific error, you need to find the error code. It is 1062 for duplicate key. Then use the result from errno() to compare with:

mysqli_query('INSERT INTO ...');
if (mysqli_errno() == 1062) {
    print 'no way!';
}

A note on programming style
You should always seek to avoid the use of magic numbers (I know, I was the one to introduce it in this answer). Instead, you could assign the known error code (1062) to a constant (e.g. MYSQLI_CODE_DUPLICATE_KEY). This will make your code easier to maintain as the condition in the if statement is still readable in a few months when the meaning of 1062 has faded from memory :)

You can check the return value from mysql_query when you do the insert.

$result = mysql_query("INSERT INTO mytable VALUES ('dupe')");

if (!$result) {
    echo "Enter a different value";
} else {
    echo "Save successful.";
}