Multi-walled carbon nanotubes (MWNTs) were synthesized on different substrates (bare Si and SiO2/Si substrate) to investigate dye-sensitized solar cell (DSSC) applications as counter electrode materials. The synthesis of MWNTs samples used identical conditions of a Fe catalyst created by thermal chemical vapor deposition at 900 oC. It was found that the diameter of the MWNTs on the Si substrate sample is approximately 5~10 nm larger than that of a SiO2/Si substrate sample. Moreover, MWNTs on a Si substrate sample were well-crystallized in terms of their Raman spectrum. In addition, the MWNTs on Si substrate sample show an enhanced redox reaction, as observed through a smaller interface resistance and faster reaction rates in the EIS spectrum. The results show that DSSCs with a MWNT counter electrode on a bare Si substrate sample demonstrate energy conversion efficiency in excess of 1.4 %.