We have successfully fabricated insoluble polymer-metal complex [{Cu-2(mu-Br)(2)(PPh3)(2)}(mu-bpy)](n) (bpy = 4, 4'-bipyridine) nanocrystals by developing already-established heterogeneous reaction process, which clearly showluminescence in solid state. Photochromic azopyridine was also adsorbed and modified on the surface of polymer-metal complex nanocrystals through applying the improved heterogeneous reaction process. Interestingly, the obtained azopyridine-modified polymermetal complex nanocrystals emitted photoresponsive fluorescence by alternative photoisomerization of azopyridine on the nanocrystals surface.