The web services do allow a loosely coupled architecture. With RMI, you have to make sure that the class definitions stay in sync in all application instances, which means that you always have to deploy all of them at the same time even if only one of them is changed (not necessarily, but it is required quite often because of serial UUIDs and whatnot)
Also it is not very scalable, which might be an issue if you want to have load balancers.
In my mind RMI works best for smaller, local applications, that are not internet-related but still need to be decoupled. I've used it to have a java application that handles electronic communications and I was quite satisfied with the results. For other applications that require more complex deployment and work across the internet, I rather use web services.
