The invention discloses a method of extracting lithium from electrolytic aluminium waste residues. The method comprises the following steps of performing a reaction on the electrolytic aluminium waste residues containing the lithium and concentrated sulfuric acid under the condition of 200 to 400 DEG C, and a mixture A is obtained; adding water into the mixture A, filtering after leaching to obtain filtrate A and a filter residue A; adding the filtrate A into sodium carbonate, and performing an alkaline hydrolysis reaction under the condition of 20 to 40 DEG C, then filtering to obtain filtrate B and a filter residue B; adding water into the filter residue B to prepare slurry, then adding lime into the slurry for a causticizing reaction, then filtering to obtain filtrate C and a filter residue C; feeding CO2 into the filtrate C in step 4) for a carbonization reaction, then filtering, washing, drying so as to obtain the lithium. The content of impurity ions in the obtained cell grade lithium carbonate is low, the quality of a product is excellent, and the problems of low yield, high production cost, weak market competitiveness when the lithium is extracted from ore to prepare the cell grade lithium carbonate at present are solved; a new process that a high value-added and high quality lithium product is produced by low-grade lithium resources is developed, the process is simple, the industrialized operation is liable to be realized, and the economic and social benefit is remarkable.