Zinc-tin oxide (ZTO) nanostructures appear as one of the most promising material systems for a new generation of nanodevices. In this work, a microwave-assisted hydrothermal synthesis to produce different shapes of Zn2SnO4 nanostructures (nanoparticles, octahedrons and nanoplates) is presented. Reproducible and homogeneous results were obtained with the advantage of reducing up to 20 h the synthesis time when compared to using a conventional oven. Furthermore, the photocatalytic activity of the Zn2SnO4 nanostructures in the degradation of rhodamine B under UV light was studied. Zn2SnO4 nanoparticles demonstrated better performance with >90% of degradation being achieved in 2.5 h.