Herein, Cu2O@CuO core-shell nanostars were prepared via a solution-processed method. High-resolution transmission electron microscopy and X-ray diffraction analyses confirmed that the Cu2O nanostars were consistently enclosed by a CuO layer. Dibromo (DB)-3,4-ethylenedioxythiphene (EDOT) monomer was prepared from commercially available 3,4-ethylenedioxythiphene via a common bromination method. The Cu2O@CuO core-shell nanostars were blended with the DBEDOT monomer and heated to 70°C to form a nano-hybrid hole transport material (HTM) for application in solid-state dye-sensitized solar cells (ssDSCs). The nanohybrid is systematically characterized through scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform spectroscopy. The photovoltaic performance of the ssDSCs was optimized by varying the Cu2O@CuO core-shell nanostars concentration in the nanohybrid HTM from 1 to 3 wt%, while maintaining the concentration of the DBEDOT monomer at 1wt%. In addition, the electrochemical properties of the nanohybrid HTM were explored through electrochemical impedance spectrometry measurements. Among the analyzed samples, the 1 wt% Cu2O@CuO core-shell nanostars in the nanohybrid HTM show the best efficiency. This method establishes the possibility of applying high-performance organic/inorganic-based nanohybrid HTMs in ssDSCs.