In this work, through the coordination of C3 symmetric azopyridine ligands and Ag(i), coordination polymers with azo groups on the main chain were prepared. The trans coordination polymer formed an organogel with a network of nanofibers at low critical gelation concentrations, and it exhibited the abilities of self-healing and multi-stimuli response to heating, light, mechanical shearing, and chemicals due to the presence of dynamic coordinating bonds. On the other hand, the cis coordination polymer was found to assemble into nanoparticles to give a responsive colloid, which can produce fibrous precipitation in several days upon visible light irradiation due to the isomerization of the azo groups. This work provides a novel example for the design of a multi-responsive organogel and colloid based on the structural transformation of coordination polymers.