Ultrasmall W18O49 NPs were synthesized by a facile hydrothermal route. Octadecylamine was used as both capping and reducing agent. The XRD patterns revealed formation of monoclinic primitive phase of W18O49. The TEM images showed that the material were well dispersed with sizes from 5 to 7 nm. The synthesized NPs exhibited pronounced photocatalytic activity towards MB degradation.