The asymmetrical zinc phthalocyanine–multiwalled carbon nanotube hybrid material (aZnPc–MWCNT) were successfully prepared by in situ click chemistry of 4-(m-tolyloxygen)-5-nitrophthalonitrile and 4-azide-phthalonitrile modified MWCNT precursors in the Cu(I)/DBU catalyst system. In situ click chemistry reactions and covalent bonds between aZnPc and MWCNT were confirmed by FT-IR, UV–Vis and fluorescence spectra. The aZnPc–MWCNT red-shifted 12–690 nm compared with pristine ZnPc. The microstructure and morphology of aZnPc–MWCNT were investigated by TEM, SEM and AFM. The solubility of aZnPc–MWCNT could be significantly improved. After the ZnPc were uniformly distributed on the surface of MWCNTs, the aggregation of aZnPc–MWCNT was significantly reduced. The thermal degradation temperature of aZnPc–MWCNT was 72.8 °C higher than that of pristine ZnPc. TG results also indicated that the ZnPc content of aZnPc–MWCNT is 14.4%. It is expected that novel organic–inorganic donor–acceptor hybrid material possessing good solubility, optical and thermal stability properties would be obtained, and new materials for the preparation of organic electronic devices should be provided.