Preparation of nanomaterials with various morphologies and exploiting their novel physical properties are of vital importance in nanoscientific field. Similarly to the III-N compound semiconductors, Si3N4 nanostructures also could be potentially used for making optoelectronic devices. In this paper, we report on an improved Fe-catalyzed chemical vapour deposition method for synthesizing ultra-long α-Si3N4 nanobelts along with a few nanowires and nanobranches on a carbon felt substrate. The ultra-long α-Si3N4 nanobelts grew via a combined VLS-base and nanobranches via a combined double-stage VLS-base and VS-tip mechanism, as well as nanowires via VLS-tip mechanism. The three individual nanostructures showed variant optical properties as revealed by a cathodoluminescence spectroscopy. A single α-Si3N4 nanobelt or nanobranch gave a strong UV-blue emission band as well as a broad red emission, whereas a single α-Si3N4 nanowire exhibited only a broad UV-blue emission. The results reported would be useful in developing new photoelectric nanodevices with tailorable or tunable properties.