Pb(Mg1/3Nb2/3)O-3 materials have been synthesized using sol-gel, freeze-drying or spray-pyrolysis techniques. The as-prepared powders were of an amorphous form which could be converted into a crystalline form by calcination. The pyrochlore phase was inevitably formed with an accompanying perovskite phase. As the calcining temperature increased, greater proportions of the desired perovskite phase occurred. The residual pyrochlore phase could be completely transformed into the perovskite phase when the powders were prepared via freeze-drying or by a spray-pyrolysis method. The maximum proportion of the pyrochlore phase was, however, only 92% when the powders were synthesized by a sol-gel route. Thermal gravimetric analysis/differential thermal analysis (TGA/DTA) and infrared transmission spectroscopy (FTIR) indicated that Mg(OEt)(2) and Nb(OEt)(5) formed a double alkoxide but Pb(OAc)(2) formed separate clusters during the hydrolysis of the solution in the sol-gel process. Inhomogeneous mixing meant that the intermediate phase formed was rather difficult to eliminate completely. Homogeneous mixing was preserved when the solution was directly freeze dried or spray pyrolysed. The size of the preferentially formed pyrochlore phase was very fine and further transformation was feasible. Pb(Mg1/3Nb2/3)O-3 materials, free of the pyrochlore phase, could therefore be obtained.