Batteries are essential for the electrification of transport and the replacement of internal combustion engines. Thermodynamics was largely established with the development of the engines, and this knowledge has been applied to batteries for years. In particular, entropy profiles are sensitive to structural changes and are useful for diagnosing and understanding battery ageing. However, entropy profiling of aged batteries is mainly limited to the potentiometric method, which makes the technique in situ and time-consuming. Herein, we rely on optical fiber calorimetry to perform operando entropy profiling of commercial sodium-ion cells. Firstly, we directly compare the entropy profile of sodium-ion Na 3 V 2 (PO 4 ) 2 F 3 /hard carbon (NVPF/HC) chemistry against those of commercialized lithium-ion chemistries, highlighting the uniqueness of NVPF/HC chemistry in battery thermal management. Operando entropy profiling of NVPF/HC chemistry further elucidates the structural degradations that take place during cycling and provide features that can be important indicators of the battery’s state of health. This work reintroduces thermodynamic analyses as a valuable tool for batteries and spotlights the new horizons offered by the convergence of battery sensing, thermodynamics, and other disciplines.