We describe the cross-linking of poly(4-styrene-sulfonic acid) (PSS) by exposure to ultraviolet (UV) light (λ = 255 nm) under a vacuum. Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) showed that the photo-crosslinking of PSS resulted from coupling between radicals that were generated in the polymer chains by UV excitation. The photo-cross-linkable characteristics of PSS were employed to fabricate solution-processable, photopatternable, and conductive PSS-wrapped multiwalled carbon nanotube (MWNT) composite thin films by wrapping MWNTs with PSS in water. During photo-cross-linking, the work function of the PSS-wrapped MWNTs decreased from 4.83 to 4.53 eV following cleavage of a significant number of sulfonic acid groups. Despite the decreased work function of the PSS-wrapped MWNTs, the photopatterned PSS-wrapped MWNTs produced good source/drain electrodes for OFETs, yielding a mobility (0.134 ± 0.056 cm²/(V s)) for the TIPS-PEN field-effect transistors fabricated using PSS-wrapped MWNTs as source/drain electrodes that was higher than the mobility of gold-based transistors (0.011 ± 0.004 cm²/(V s)).