Ultraviolet (UV), visible, and near‐infrared (NIR) broadband organic photodetectors are fabricated by sequential solution‐based thin film coatings of a polymer electron blocking layer (EBL) and a polymer photoactive layer. To avoid damage to a preceding polymer EBL during a subsequent solution‐based film coating of a polymer photoactive layer due to lack of solvent orthogonality, 2‐(((4‐azido‐2,3,5,6‐tetrafluorobenzoyl)oxy)methyl)−2‐ethylpropane‐1,3‐diyl bis(4‐azido‐2,3,5,6‐tetrafluorobenzoate) (FPA‐3F) is used as a novel organic cross‐linking agent activated by UV irradiation with a wavelength of 254 nm. Solution‐processed poly[N,N′‐bis(4‐butylphenyl)‐N,N′‐bis(phenyl)‐benzidine] (poly‐TPD) films, which are cross‐linked with a FPA‐3F photocrosslinker, are used for a preceding polymer EBL. A ternary blend film composed of PTB7‐Th, COi8DFIC, and PC71BM is used as a NIR‐sensitive organic photoactive layer with strong photosensitivity in multispectral (UV–visible–NIR) wavelengths of 300–1,050 nm. Poly‐TPD films are successfully cross‐linked even with a very small amount of 1 wt% FPA‐3F. Small amounts of FPA‐3F have little detrimental effect on the electrical and optoelectronic properties of the cross‐linked poly‐TPD EBL. Finally, organic NIR photodetectors with a poly‐TPD EBL cross‐linked by the small addition of FPA‐3F (1 wt%) show the detectivity values higher than 1 × 1012 Jones for the entire UV–visible–NIR wavelengths from 300 nm to 1050 nm, and the maximum detectivity values of 1.41 × 1013 Jones and 8.90 × 1012 Jones at the NIR wavelengths of 900 and 1000 nm, respectively.