In this study, we present some design suggestions for all-polymer solar cells by utilizing device simulation. The polymer solar cell under investigation is formed by a photoactive film of a blend comprising PBDB-T as a polymer donor and PZT as a polymerized small molecule acceptor. The initial cell is based on a fabricated cell whose structure is ITO/PEDOT:PSS/PBDB-T:PZT/PFN-Br/Ag, which has a power conversion efficiency (PCE) of about 14.9%. A calibration procedure is then performed by comparing the simulation results with experimental data to confirm the simulation models, and the material parameters, implemented in the SCAPS (Solar Cell Capacitance Simulator) simulator. To boost the open circuit voltage, we investigate a group of hole transport layer (HTL) materials. An HTL of CuI or P3HT, that may replace the PEDOT:PSS, results in a PCE of higher than 20%. However, this enhanced efficiency results in a minor S-shape curve in the current density-voltage (J-V) characteristic. So, to suppress the possibility of the appearance of an S-curve, we propose a double HTL structure, for which the simulation shows a higher PCE with a suppressed kink phenomenon due to the proper band alignment. Moreover, the designed cell is investigated when subjected to a low light intensity, and the cell shows a good performance, signifying the cell’s suitability for indoor applications. The results of this simulation study can add to the potential development of highly efficient all-polymer solar cells.