We show in this Communication that the combination of Rietveld and pair distribution function (PDF) analyses allows unique insight into the nature and driving force of the phase transition of alpha-AlF3, which was not available from conventional structural analysis methods alone. The use of image plate technology allows structural changes to be followed in "real time" and reduces the time required to collect high-resolution PDF data from hours (with a conventional solid state detector) to seconds. This methodology produces raw data that can simultaneously be analyzed by both Rietveld and PDF analysis.