The present invention relates to a solid rocket engine propellant lining layer material and a preparation method thereof, and belongs to the field of solid rocket engine lining layer material preparation. According to the present invention, azido-terminated polybutadiene is adopted as a polymer prepolymer, a multi-alkynyl compound is adopted as a curing agent, a plasticizer, a solid filler and a process auxiliary agent are added, and an inter-azido/alkynyl click chemistry reaction is used to prepare the triazole five-membered ring cross-linked low-polarity polybutadiene lining layer material, such that the migration performance of the polar nitrate plasticizer of the NEPE composite propellant in the lining layer material is effectively inhibited; and the obtained solid rocket engine propellant lining layer material can be subjected to curing molding within the temperature of 50-70 DEG C, the reaction conditions are mild, the obtained lining layer material has low polarity, the disadvantages of the propellant lining layer material preparation through the cross-linking of polyurethane and polybutadiene are overcome, and the propellant lining layer material preparation method is broadened.