In the present study, tetramethylammonium hydroquinone (HQ)/benzoquinone (BQ) were developed for use as a redox couple, with poly(3,4-ethylenedioxythiophene) (PEDOT) and multiwalled carbon nanotubes (MWNT) being proposed for use as counter electrode (CE) catalysts in dye-sensitized solar cells (DSSCs). Both metal-complex N719 and metal-free organic dye CM309 were employed to fabricate devices. For the devices sensitized by N719, when using PEDOT and MWNT CEs, power conversion efficiencies (PCE) of 5.2 and 4.9% were obtained, respectively, which were much higher than that of the device using the traditional Pt CE (4.7%) when HQ/BQ electrolyte was employed. However, with the HQ/BQ redox shuttle, the efficiency of the devices sensitized by N719 is much lower than that of the devices when the traditional I(-)/I3(-) based electrolyte and Pt CE were employed (7.9%). While for the CM309 sensitized solar cells, when the HQ/BQ redox shuttle was employed, PEDOT and MWNT performed much better than Pt, the DSSC using the PEDOT CE showed an efficiency of 6.2%, which was close to that of the DSSC using the traditional I(-)/I3(-) electrolyte and Pt CE (6.3%).