Mechanoresponsive luminescent (MRL) materials change their emission color upon application of external forces. Many dyes with MRL behavior are known, but they normally do not display useful mechanical properties. Here, we introduce a new approach to overcome this problem, which relies on combining MRL compounds with the concept of supramolecular polymerization. As a first embodiment, a cyano-substituted oligo(p-phenylenevinylene), whose MRL behavior is associated with different solid-state assemblies, was derivatized with two ureido-4-pyrimidinone groups, which support the formation of a dynamic supramolecular polymer. The new material displays the thermomechanical characteristics of a supramolecular polymer glass, offers three different emission colors in the solid state, and exhibits both MRL and thermoresponsive luminescent behavior.