Copper phosphide (Cu3P) nanotubes were successfully synthesised via a facile solvothermal route. The characterisation and analysis results indicate that the as-prepared sample is composed of a large quantity of Cu3P nanotubes with the mean diameter of about 100 nm, some nanotubes pass across each other and form the right angle morphology. Moreover, these nanotubes (sample II) can easily be changed to some irregular particles (sample I) or hollow spherical nanostructures (sample III) when the amount of cetyltrimethylammonium bromide is controlled in the experiments. Choosing methylene blue (MB) as a typical organic dye, Cu3P nanotubes exhibit a good photocatalytic activity, which may be that its large specific surface area enhances the oxidation-reduction ability of electron–hole.