It is demonstrated for the first time that significant enhancement of photoelectrochemical performance could be achieved by using microwave-assisted annealing for the fabrication of alpha-Fe2O3 thin films. The process can also lead to significant energy savings (>60% when compared with conventional methods). Different types of Fe thin films were oxidized using both microwave and conventional heating techniques. The photoelectrochemical performance of electrodeposited, undoped and Si-doped iron oxide samples showed that microwave-annealing resulted in superior structural and performance enhancements. The photocurrent densities obtained from microwave annealed samples are among the highest values reported for alpha-Fe2O3 photoelectrodes fabricated at low temperatures and short times; the highest photocurrent density at 0.55 V vs. V-Ag/AgCl, before the dark current onset, was 450 mu A cm(-2) for the Si-doped films annealed at 270 degrees C for 15 min using microwave irradiation (and 180 mu A cm(-2) at 0.23 V vs. V-Ag/AgCl) while conventional annealing at the same temperature resulted in samples with negligible (3 mu A cm(-2)) photoactivity. In contrast, a 450 degrees C/15 min conventional heat treatment only resulted in a film with 25% lower photocurrent density than that of the microwave annealed sample. The improved performance is attributed to the lower processing temperatures and rapidity of the microwave method that help to retain the nanostructure of the thin films whilst restricting the grain growth to a minimum. The lower processing temperature requirements of the microwave process can also open up the possibility of fabricating hematite thin films on conducting, flexible, plastic electronic substrates. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.