A chain-shattering polymer (CSP) has been proposed as a microdispersive solid-phase extraction (μdSPE) sorbent in a proof-of-concept study of degradable materials for analytical purposes. The responsive CSP was synthesized from 1,3,5-tris(bromomethyl)-2-nitrobenzene acting as the self-immolative trigger responsive unit and 2,6-naphthalenedicarboxylic acid as aromatic linker to enhance noncovalent aromatic interactions with the analytes. The CSP was characterized and applied as a μdSPE sorbent of a group of plasticizers, which were selected as model analytes, from different types of environmental water samples (tap, waste, and spring waters). Gas chromatography coupled to mass spectrometry detection was used for analyte determination. Mean recovery values were in the range of 80%-118% with RSD values below 22%. After the extraction, the polymer could be efficiently degraded by UV irradiation or by chemical reduction, recovering the aromatic linker. This work has proved the potential of CSPs as recyclable sorbents, paving the way to more environmentally benign analytical procedures.