The use of ionic liquids as additives and an economic and environmentally benign alternative to conventional inorganic and organic additives in poly(vinyl chloride) (PVC) formulation is investigated by using thermogravimetric analysis. The present study deals with an elegant exploration of the resulting thermal profiles to disclose the pattern of thermal degradation for N-butylpyridinium hexafluorophosphate and PVC formulation as well. Furthermore, non-isothermal kinetic investigations providing sound information about kinetic parameters, such as activation energy and frequency factor by using the Coats–Redfern equation in the temperature range of 593–663 K for N-butylpyridinium hexafluorophosphate and 423–473 K for the resulting PVC formulation were performed.