Ultralong, highly branched Sn-doped zinc oxide (ZnO) nanostructures were fabricated using a simple substrate-free chemical vapor deposition (CVD) method. The nanostructures exhibited efficient photocatalytic activities in degradation of methylene blue (MB) under natural sunlight. 100% of MB with the concentration of 10 mg/L could be completely removed within 36 minutes. Possible reasons for the enhanced photocatalytic effect were analyzed.