AbstractStrategies for visualizing stress within polymeric materials are of growing interest during the past decade. In this paper, stress‐sensing materials, triggered by a mechanoresponsive catalytic system based on latent copper(I)bis(N‐heterocyclic carbene) mechanophores, are reported, which can be activated by compression force to trigger a fluorogenic copper(I)‐catalyzed alkyne/azide “click” cycloaddition reaction, activating a fluorescent dye useful for stress‐sensing applications in bulk polymeric materials. The focus is placed on the polymeric architecture, which is responsible for an efficient stress transmission, revealing the greatest activation for network‐based mechanocatalysts, observing “click” conversions up to 44%, while chain‐extended and linear mechanocatalysts activate either in a less efficient manner or are not completely latent in the initial state. The developed catalysts enable “irreversible” mechanochromic systems for stress‐sensing devices.