An electrochemical method has been developed to analyze dye absorption on the aligned carbon nanofiber arrays coated with TiO2 nanoneedles for dyesensitized solar cell. The unique nanostructure with the roughness factor of 90.6 provides a large effective surface area for dye adsorption. The experimental results showed that the dye molecules cover 39.7% of the TiO2 surface area which influences the performance of dye-sensitized solar cell. The electrochemical method provides the information of the coverage of dye molecules which is a key issue to optimize solar cell performance.