The invention discloses a recycling and utilization method of waste cathode carbon block of an aluminum electrolytic tank. The method comprises the following steps: performing crushing, color selection, pulverization and ball milling on a waste cathode carbon block raw material of the aluminum electrolytic tank to obtain carbon powder, and then blending the carbon powder with a 5A or 10X type zeolite molecular sieve which accounts for 5 to 20 percent by mass of the carbon powder and has a particle size less than 2 mm, performing thermal treatment at 800 to 1,600 DEG C for 30 to 120 min, adding98 percent by weight of concentrated sulfuric acid with temperature of 80 to 120 DEG C into a fluorine-containing solid product, and introducing generated HF gas into deionized water for absorption and condensation to obtain a hydrofluoric acid product. According to the recycling and utilization method, the zeolite molecular sieve is used as a thermal treatment reaction material and also achievesthe effects of a catalyst and a dispersant; the process is advanced, and the advantages are obvious; and on the premise of realizing 'zero discharging' of harmful gas, a high-added-value hydrofluoricacid product is obtained, and the environmental benefit and the economical benefit are outstanding.