ABSTRACT: In this paper, we present the use of a disubstituted polyacetylene with high thermal stability and quantum yield as a fluorescence label for the identification, tracing, recycling, and eventually anti-counterfeiting applications of thermoplastics. A new method was developed for the dispersion of poly[1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene] (PTMSDPA) into polymer blends. For such purposes, four representative commodity plastics were selected, i.e., polypropylene, low-density polyethylene, poly(methyl methacrylate), and polylactide. Polymer recycling was mimicked by two reprocessing cycles of the material, which imparted intensive luminescence to the labelled polymer blends when excited by proper illumination. The concentration of the labelling polymer in the matrices was approximately a few tens ppm by weight. Luminescence was visible to the naked eye and survived the simulated recycling successfully. In addition, luminescence emission maxima were correlated with polymer polarity and glass transition temperature, showing a marked blueshift in luminescence emission maxima with the increase in processing temperature and time. This blueshift results from the dispersion of the labelling polymer into the labelled polymer matrix. During processing, the polyacetylene chains disentangled, thereby suppressing their intermolecular interactions. Moreover, shear forces imposed during viscous polymer melt mixing enforced conformational changes, which shortened the average conjugation length of PTMSDPA chain segments. Combined, these two mechanisms shift the luminescence of the probe from a solid- to a more solution-like state. Thus, PTMSDPA can be used as a luminescent probe for dispersion quality, polymer blend homogeneity, and processing history, in addition to the identification, tracing, and recycling of thermoplastics.