Will my ConnectedTV Apps be available worldwide regardless of countries and/or geographical regions?

Yes, that is the default publishing setup, unless you want GeoIP blocking installed in order to block specific regions. Unless specified otherwise, all apps will be available to all viewers worldwide. The big advantage of ConnectedTV platforms such as Roku, FireTV, AndroidTV, GoogleTV etc. is that they have no language restriction or country restrictions and are available worldwide. This will be a huge benefit to any organization and their goals.