Designing an environment-friendly delamination process for an end-of-life (EoL) composite cathode is a crucial step in direct cathode recycling. In this study, the green solvent dimethyl isosorbide (DMI) is explored to extract cathode active materials (AMs) from the Al current collector via dissolving the polyvinylidene fluoride (PVDF) binder. Mechanistic insight suggests that binder removal from the Al substrate proceeds via reducing polymer interchain interaction through DMI penetrating into the PVDF crystalline region. Polymer-solvent interaction may increase via establishing hydrogen bond between PVDF and DMI, which facilitates binder removal. Analytical characterizations including 1H NMR, FTIR, XRD and SEM-EDS reveal that the molecular, micro, and crystal structures of the recovered cathode AMs, PVDF and Al foil are preserved. This finding is expected to provide a replacement for the toxic organic solvent N-methylpyrrolidone (NMP) and offers an effective, ecofriendly, and sustainable direct cathode recycling approach for spent Li-ion batteries.