Population growth, depletion of world resources and persistent toxic chemical production underline the need to seek new smart materials from inexpensive, biodegradable, and renewable feedstocks. Hence, “metal-free” ring-opening copolymerization to convert biomass carvone-based monomers into non-conventional luminescent biopolymers is considered a sustainable approach to achieve these goals. The non-conventional emission was studied in terms of steady-state and time-resolved spectroscopy in order to unravel the structure-properties for different carvone-based copolymers. The results highlighted the importance of the final copolymer folding structure as well as its environment in luminescent behavior (cluster-triggered emission). In all cases, their luminescent behavior is sensitive to small temperature fluctuations (where the minimum detected temperature is Tm ∼ 2 °C and relative sensitivity is Sr ∼ 6% °C) even at the microscopic scale, which endows these materials a great potential as thermosensitive smart polymers for photothermal imaging.