Two new polyimide based porous covalent organic frameworks (PI-COF 201 and PI-COF 202) were synthesized in high yields by directly heating mixtures of melamine and pyromellitic dianhydride and naphthalenetetracarboxylic dianhydride in a N₂ atmosphere, respectively. Their structures and properties were characterized using elemental analysis, Fourier transform infrared spectra, X-ray photoelectron spectroscopy, X-ray powder diffraction, N₂ adsorption–desorption and scanning electron microscopy and their fluorescence properties were studied in detail. These two COFs emitted strong fluorescence in appropriate solvents that originated from the π* → n transition caused by the high electro-delocalization and inherently rigid structure of the COF materials. The strong quenching effects of Fe³⁺ on the fluorescence of the COFs allowed selective chemosensing for Fe³⁺.