A tellurium-doped carbon nanomaterial (Te-MC(P)) was newly developed by the soft-templated carbonization of the PAN-b-PBA copolymer with poly(3-hexyltellurophene). Te-MC(P) was characterized with various characterization methods, including the nitrogen sorption isotherm measurement (BET), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDS), which reveal that the Te atoms are homogeneously dispersed in the three-dimensional hierarchical, graphite-like mesoporous carbon matrix with a Te doping level of 0.27 atom %. Based on the characterization results, the electrocatalytic ability of Te-MC(P) was evaluated by using a symmetrical dummy cell test with both Co(bpy)32+/3+ (bpy = 2,2'-bipyridine) and I-/I3- redox electrolytes as counter electrodes (CEs). The Te-MC(P) CEs showed remarkably lower charge-transfer resistance (Rct) values by approximately 10 times in the electrochemical impedance spectroscopy (EIS) measurement, compared to the counterpart platinum (Pt) and the tellurium-based material (Te-MC(A)), prepared with a telluric acid precursor that has a lower Te doping level of 0.15 at%. As a result, the excellent electrocatalytic ability of Te-MC(P) resulted in the improvement of photovoltaic performance. The power conversion efficiencies (PCEs) of Te-MC(P)-based dye-sensitized solar cells (DSSCs) were 12.69% for the Co(bpy)32+/3+ redox electrolyte with the SGT-021 porphyrin dye and 9.73% for the I-/I3- redox electrolyte with the N719 ruthenium dye. Furthermore, Te- MC(P) CEs exhibited remarkable electrochemical stability in the two redox electrolytes. These results could suggest that the Te-MC(P) CE is one of the best promising alternatives to Pt CEs as a low-cost, highly stable and efficient electrocatalytic CE for practical applications.