The invention discloses a polishing agent for precise polishing of a high-alloy-aluminium metallographic sample. The polishing agent comprises water, corundum particles and sodium hydroxide, namely, sodium hydroxide, which is an chemical aggressive agent, is added in corundum polishing suspension formed by water and corundum powder, so that not only can the problems of disturbance layers and scratches of mechanical polishing be avoid, but also the problem of disappearance or protrusion of part of phase corrosion of electrolysis and chemical polishing can be avoid, further, the circumstance of observation illusion can be avoided; and meanwhile, the time for precise polishing can be shortened greatly, so that the purpose of preparing high-quality metallographic samples quickly can be achieved. When the agent for precise polishing of a high-alloy-aluminium metallographic sample, provided by the invention, is in use, a polisher is started first, then a reagent bottle filled with the polishing agent is shaken until the polisher runs normally so as to ensure that the polishing agent is mixed uniformly, and the reagent bottle is compressed to enable the polishing agent to be uniformly sprayed onto polishing fabric of the polisher. The invention further discloses a precise polishing method for a high-alloy-aluminium metallographic sample.