Vishwas Lele gave an excellent presentation at CAPAREA last night on bringing together Windows Communication Framework and Workflow Framework. Vishwas is the CTO at AIS and also the Microsoft Regional Director for the Washington, DC, area.
One of the interesting suggestions for why you would want to do this is that the technology lets you chain together web services in a workflow so that the service calls occur in a proper order. Web services by themselves are inherently stateless - unless you build the infrastructure to manage state in them. But with WCF and WF, combining these two technologies together you get that infrastructure right out of the box.
