A new strategy for synthesizing multisubstituted poly(naphthopyran)s (PNPs) with novel functionalities was described. The cascade oxidative polyannulation of benzoylacetonitrile and internal II diynes are catalyzed by [RhCp*Cl-2](2) and Cu(II) acetate in dimethylformamide at 90 degrees C, generating PNPs with high molecular weight of up to 19 300 in excellent yields (isolation yield up to 96.4%). This polymerization method enjoys the remarkable advantages of high reaction rate, high efficiency, and atom-economy. All of the polymers show good solubility in common organic solvents and high thermal stability (degradation temperature up to 431 degrees C). The thin films of PNPs display high refractive indices (1.5137-1.7524) in a wide wavelength range of 450-1600 nm. PNP containing tetraphenylethene units can be utilized to generate a well-resolved nanoscale photopattern by UV irradiation of its film through a copper mask. The PNPs exhibit the phenomena of mechanochromism and vapochromism: their emission is turned on upon scratching and solvent fuming their solid powders. Such attributes allow the polymers to be used as security materials or fluorescent indicators in various fields.