I have a PHP form which enters data into my MySQL database. My primary key is one of the user-entered values. When the user enters a value that already exists in the table,
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 :)