A novel dye-sensitized solar cell (DSSC) architecture based on vertically aligned carbon nanofibers coated with a thin nanoneedle-textured anatase TiO2 film is demonstrated. An encouraging overall conversion efficiency of approximately 1.09% and a rather high open-circuit voltage of approximately 0.64 V have been achieved. The efficient charge separation at the TiO2-CNF junction and the large outer TiO2 surface of this core-shell architecture provide new methods to tune the materials and interfaces in solar cells.