In a structured interview, each candidate is asked similar questions in a predetermined format. Emphasis tends to be on your past experience and assets you can bring to company. Typically, the interviewer records your answers, which are potentially scored on a standard grid.
Unstructured interviews are much more casual and unrehearsed. They depend on free flowing conversation which tends to focus on your personal qualities as they relate to the work. Questions about skills and strengths can be asked and should be answered as formally as in a structured interview.
Unstructured interviews may be so by design of the interviewer, or may be so due to the spontaneity of the event—you might find yourself in an unstructured interview after being introduced to a potential employer by a friend, or while dropping off a resume in person at a location in which you wish to work.
Conversation and exchange is more important than the particular questions being asked. In such an interview it is important to hold on to the main points you want this employer to hear, and weave them into the conversation. Try to relax in the format – be polite, mature and sociable.