The discovery of a series of coupling reactions between various building blocks has driven the development of porous organic polymers, but the common usage of expensive and air-sensitive organometallic catalysts and complex procedures in harsh syntheses has limited their expansion. A microporous hypercrosslinked polymer (HCP) was synthesized by polymerizing a naphthalene monomer and a 1,4-dimethoxybenzene crosslinker using Friedel–Crafts alkylation over an FeCl₃ catalyst and imprinted with 3,5-dinitrosalicylic acid (DNS). The DNS-molecularly-imprinted HCPs (MIHCPs) were characterized as having IUPAC Type I mesoporosity, a specific surface area of 1134 m² g⁻¹, a monolayer adsorption capacity of 116 cm² g⁻¹, pore sizes ranging from 5 to 8.5 Å, amorphous frameworks, and distinctive absorption and emission bands by N₂ adsorption/desorption analyses, scanning and transmission electron microscopies, and FTIR, UV–Vis, and fluorescence spectrometries. The π-conjugated imprinted framework endowed the MIHCPs with 405-nm fluorescent emission at a 330-nm excitation and dynamic quenching, which was confirmed by changes in fluorescence lifetime and followed a linear Stern-Volmer plot against 1.0–200 μM DNS template molecules under optimized conditions of a pH 7.0 buffer, an MIHCP concentration of 125 μg mL⁻¹, and a 3.0-min equilibration time. The MIHCPs exhibited a high imprinted factor of 8.7 against nonimprinted HCP and a selectivity of 8.63 against reduced DNS, which enabled fluorometric detection of DNS molecules produced by the hydrolysis of starch with microbial, salivary, and pancreatic α-amylases and the subsequent redox incubation with the DNS oxidant. The fluorometric measurement of α-amylase activity was higher in accuracy and precision (RSD: 2.6–2.8% vs. 3.9–4.0%) than conventional UV–Vis spectrometry because the excellent fluorescent sensitivity and imprinting selectivity of the MIHCP probes enabled the use of higher dilution factors with weaker matrix effects.