Pyrolysis of waste low-density polyethylene (LDPE) is considered to be a highly efficient, promising treatment method. This work aims to investigate the kinetics of LDPE pyrolysis using three model-free methods (Friedman, Flynn-Wall-Qzawa (FWO), and Kissinger-Akahira-Sunose (KAS)), two model-fitting methods (Arrhenius and Coats-Redfern), as well as to develop, for the first time, a highly efficient artificial neural network (ANN) model to predict the kinetic parameters of LDPE pyrolysis. Thermogravimetric (TG) and derivative thermogravimetric (DTG) thermograms at 5, 10, 20 and 40 K min−1 showed only a single pyrolysis zone, implying a single reaction. The values of the kinetic parameters (E and A) of LDPE pyrolysis have been calculated at different conversions by three model-free methods and the average values of the obtained activation energies are in good agreement and ranging between 193 and 195 kJ mol−1. In addition, these kinetic parameters at different heating rates have been calculated using Arrhenius and Coats-Redfern methods. Moreover, a feed-forward ANN with backpropagation model, with 10 neurons in two hidden layers and logsig-logsig transfer functions, has been employed to predict the thermogravimetric analysis (TGA) kinetic data. Results showed good agreement between the ANN-predicted and experimental data (R > 0.9999). Then, the selected network topology was tested for extra new input data with a highly efficient performance.