This is how I usually connect to a MySQL database using SSL:
$db = mysqli_init();
mysqli_ssl_set(
    $db,
    NULL,
    NULL,
    '/etc/ssl/my-certs/ssl-ca.crt.pem',
    NULL,
    NULL
);
mysqli_real_connect(
    $db,
    'db.example.com',
    'john',
    '123456',
    NULL,
    NULL,
    NULL,
    MYSQLI_CLIENT_SSL
);
From what I understand, the MYSQLI_CLIENT_SSL flag is necessary to make mysqli::real_connect connect to the server using SSL. 
Today I stumbled upon the documentation for mysqli::options, and noticed that it accepts MYSQLI_OPT_SSL_VERIFY_SERVER_CERT as an option, but, alas, its description is blank. So, I wonder:
- When do I need to add 
mysqli_options($db, MYSQLI_OPT_SSL_VERIFY_SERVER_CERT, true);? - When do I need to use the 
MYSQLI_CLIENT_SSLflag? - When will I need to set both of them?