It really depends on how your application works. If the app requests a AAAA record first, and that succeeds, the client will attempt to contact the server via IPv6. If, however, the client only requests the A record, then the client will communicate with the server with IPv4.
In C programming, one could use gethostbyname2(), getaddrinfo(), or getnameinfo() to specifically request an address of type AF_INET6. Some resolver libraries can even be configured to use IPv6 by default (e.g. on FreeBSD or Linux one can add "options inet6" to /etc/resolv.conf).