Multi-walled carbon nanotubes (MWCNT) attached on ZnO quantum dots named ZnO/MWCNT composites were synthesized by a multi-steps wet chemical self-assembling technique. The morphology of ZnO/MWCNT was also studied in details. The as-prepared ZnO and ZnO/ MWCNT composites had been characterized by XRD, SEM and TEM. It was found that the co-existence of MWCNTs and ZnO in ZnO/MWCNT sample. Monodispersed ZnO nanoparticles and the MWNTs/ZnO conjunction structure can be vividly observed from TEM image. TEM image also indicated that the decoration of MWCNTs did not cause any damage to the tubular shape and the conjunction occurred at the outershell of MWCNTs. Moreover, to assess the optoelectronic properties, photoluminescence (PL) spectra were also compared between monodispersed ZnO QDs and the ZnO /MWCNT composites. The relationship between PL spectra and structure was discussed. It was shown that the particular PL behavior of ZnO in the ZnO/MWCNT had been quenched, which meant the electron transformation between the ZnO and MWCNT had happened.