This study aims to deal with the film of the counter electrode of dye-sensitized solar cells (DSSCs) and the preparation, structure and characteristics of the extract of natural dye. This study adopts different commercial carbon materials such as black lead, carbon black and self-made TiO2-MWCNT compound nanoparticle as the film of the counter electrodes. Moreover, for the preparation of natural dyes, anthocyanins and chlorophyll dyes are extracted from mulberry and pomegranate respectively. Furthermore, the extracted anthocyanins and chlorophyll are blended into cocktail dye to complete the preparation of natural dye. Results show that the photoelectric conversion efficiency of the single-layer TiO2-MWCNT counter electrode film and the cocktail dye of the DSSCs is 0.462%.