Substituted derivatives of hydroquinone/benzoquinone were studied as organic redox mediators in the electrolyte for dye-sensitized solar cells (DSSCs). Thus, di-tert-butylhydroquinone (DTHQ), thymohydroquinone (ThymHQ) and phenylhydroquinone (PhHQ), were combined with their oxidized counterparts to form the pairs DTHQ/DTBQ, ThymHQ/ThymBQ, and PhHQ/PhBQ. In general, the characteristic parameters of the DSSCs with the substituted derivatives surpassed those of the DSSC with the unsubstituted hydroquinone/benzoquinone electrolyte. The short-circuit current (J(sc)) of the devices using DTHQ/DTBQ and ThymHQ/ThymBQ (13.61 mA cm(-2) and 12.56 mA cm(-2), respectively) are comparable to the J(sc) obtained for cobalt(II/III) tris (bipyridine) as a reference electrolyte (14.54 mA cm(-2)). However, parameters such as open-circuit voltage (V-oc) and fill factor (FF) (547 mV and 0.48, respectively) are far from competitive. The best photovoltaic performance was obtained for the pair ThymHQ/ThymBQ using a triphenylamine (TPA)-based organic dye (LEG4) as sensitizer and a hybrid counter electrode with poly(3,4-ethylenedioxythiophene) (PEDOT) and graphene. These experimental conditions give under 1 sun (98%) the highest efficiency (eta = 3.19%); low-light intensities of 12.3% and 51.8% suns lead to efficiencies of 3.34% and 3.29%, respectively. Electrochemical impedance spectroscopy (EIS) revealed that the main cause for loss in photocurrent is the low recombination resistance compared to Co(II/III) as reference electrolyte. Based on the EIS analysis, a down-shift of the conduction band of TiO2 was found for all assembled devices containing the organic redox mediators, which explains the low V-oc values for these derivatives.