Hole transport material-free carbon-based perovskite solar cells (HTM-free C–PSCs) are recognized as a cost-effective and stable alternative to conventional perovskite solar cells. However, the significant energy level misalignment between the perovskite layer and the carbon counter electrode (CE) results in ineffective hole extraction and unfavorable charge recombination, which decreases the power conversion efficiency (PCE). Here, we report the introduction of metal salts (Al, Ca, and Mg) into graphite/carbon black (Gr/CB) CEs to modify the work function and enhance the hole selectivity of the CE. This modification leads to improved energy level alignment, efficient hole extraction, and reduced charge recombination. The PCE of the HTM-free C-PSC based on Al-modified Gr/CB as the CE material reached 9.91%, which is approximately 12% higher than that of devices employing unmodified Gr/CB CEs. This work demonstrates that by directly incorporating metal salts into the Gr/CB CE, the energy level alignment and hole extraction at the perovskite/carbon interface can be improved. This presents a viable method for enhancing the PCE of HTM-free C–PSCs.