Multi-walled carbon nanotubes (MWNTs) were synthesized on different substrates (bare Si and $SiO_2$/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 $900^{circ}C$. It was found that the diameter of the MWNTs on the Si substrate sample is approximately $5{sim}10nm$ larger than that of a $SiO_2$/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 %.