1,4-Bis(piperidyl)naphthalene (1,4-BPN) was employed as a cross-linker for poly(n-butyl methacrylate) gels to generate soft materials that exhibit selective fluorescence quenching and photodegradation in 1,1,1-trichloromethyl-containing chloroalkanes. In chloroform and 1,1,1-trichloroethane, 1,4-BPN is subject to efficient fluorescence quenching via the formation of exciplexes, which results in rapid photodegradation. Similarly, poly(n-butyl methacrylate) gels cross-linked with 1,4-BPN were highly fluorescent and stable in various organic solvents and chloroalkanes but exhibited less intense fluorescence and rapid photodegradation in 1,1,1trichloromethyl-containing chloroalkanes. Upon swelling in 1,1,1-trichloroethane, these gels exhibited a steep drop in the storage modulus during first 10 s of photoirradiation (lambda= 365 nm). Further photoirradiation for 10-30 min led to the decomposition cross-linker can be used for the facile preparation of diverse polymeric photodecomposition properties toward unreactive and neutral analytes. of the gels. Thus, we propose that the 1,4-BPN-based materials with synergistic fluorescence, detection, and photodecomposition properties toward unreactive and neutral analytes.