Can I choose what roles to be synced?

Yes, you can choose what roles to be synced and what not.

There are several types of roles in a WordPress site. Some are the default and some roles are custom. Like, WooCommerce has two roles – customer role and shop manager role. “Share Logins Pro” shows every type of role in the drop-down menu.

Admin can choose one or multiple roles to be synced from one site to another.

See this screenshot-