Despite the high efficiencies currently achieved with perovskite solar cells (PSCs), the need to develop stable devices, particularly in humid conditions, still remains. This study presents the synthesis of a novel photo-cross-linkable fullerene-based hole transport material named FT₁₂. For the first time, the photo-cross-linking process is applied to PSCs, resulting in the preparation of photo-cross-linked FT₁₂ (PCL FT₁₂). Regular PSCs based on C₆₀-sandwich architectures were fabricated using FT₁₂ and PCL FT₁₂ as dopant-free hole transport layers (HTLs) and compared to the reference spiro-OMeTAD. The photovoltaic results demonstrate that both FT₁₂ and PCL FT₁₂ significantly outperform pristine spiro-OMeTAD regarding device performance and stability. The comparison between devices based on FT₁₂ and PCL FT₁₂ demonstrates that the photo-cross-linking process enhances device efficiency. This improvement is primarily attributed to enhanced charge extraction, partial oxidation of the HTL, increased hole mobility, and improved layer morphology. PCL FT₁₂-based devices exhibit improved stability compared to FT₁₂ devices, primarily due to the superior moisture resistance achieved through photo-cross-linking.