the Microsoft XSD inference tool is a good, free solution. Many XML editing tools, such as XmlSpy (mentioned by @Garth Gilmour) or OxygenXML Editor also have that feature. They’re rather expensive, though. BizTalk Server also has an XSD inferring tool as well.
edit: I just discovered the .net XmlSchemaInference class, so if you’re using .net you should consider that