Effective and environmentally benign removal of polyvinylidene fluoride (PVDF) binders from spent battery electrodes remains a critical hurdle in sustainable recycling, primarily due to issues related to the mitigation of fluorinated compound emissions. This work evaluates PVDF binder removal from cathode active material using either a green solvent-based dissolution process or pyrolysis, analyzed by time-of-flight secondary ion mass spectrometry (ToF-SIMS). The solvent pretreatment involved mixing dihydrolevoglucosenone (Cyrene™) with PVDF-coated NMC811 at 100 °C, followed by hot filtration to separate the Cyrene-PVDF solution. Pyrolysis was conducted at 800 °C under an argon atmosphere. Positive ToF-SIMS spectra for Cyrene showed characteristic peaks at ketene (42 m/z) and 1,3-dioxole (86 m/z), along with intense C₂H₃O⁺, C₃H₃O⁺, C₄H₇⁺, and C₃H₅O⁺ peaks. The characteristic peaks used to identify PVDF were C₃H₂F₅⁺ (133 m/z), C₃H₂F₃⁺ (95 m/z), and C₃HF₄⁺ (113 m/z). Both processes resulted in PVDF removal, with pyrolysis demonstrating higher effectiveness. Particle agglomeration was observed in both pretreated NMC811 samples, however agglomeration was more pronounced with Cyrene pretreatment due to PVDF redeposition. Following pyrolysis, PVDF was transformed into a defluorinated carbonaceous material.