The design and synthesis of porous organic polymers for the potential application in chemical sensors re-mains a huge challenge nowadays. Herein, a porous organic polymer possessing tetrazole groups(TTZ-3) was synthe-sized via simple Schiff base chemical reaction. Thermogravimetric analysis(TGA), Fourier transform infrared spec-trometer(FTIR), solid-state 13C cross polarization/magic angle spinning nuclear magnetic resonance(CP/MAS NMR), transmission electron microscopies(TEM) and field-scanning electron microscopies(FE-SEM) were adopted to characterize the structure and morphology in detail. Significantly, the formed polymers exhibited special detection of unsaturated hydrocarbons through fluorescence enhancement based on photoactivatable 1,3-dipolar cycloaddition reactions. Furthermore, the reaction activity of different unsaturated hydrocarbons towards the polymers was investigated. This work highlights the great potential of porous organic polymers as chemical sensors in realizing environmental pollution monitoring and reducing the incidence of disease, such as chronic obstructive pulmonary disease.