The invention relates to an underwater solventless epoxy anti-corrosive coating and a preparation method thereof. The coating contains A component and B component and comprises the following components by weight percent: 20-25% of epoxy resin E-51, 12-17% of epoxy resin E-44, 3-8% of epoxy active diluent, 3.5-5% of plasticizer, 10-16% of talcum powder, 10-15% of sericite powder, 1.0-1.6% of thixotropic agent, 2-4% of titanium dioxide, 0.5-1.0% of coupling agent, 0.5-1.2% of dispersant, 0.5-1.2% of defoaming agent, 0.1-0.5% of carbon black, 12-15% of 1085 curing agent and 5-8% of 810 curing agent; wherein, B component comprises 1085 curing agent and 810 curing agent and the remainder is A component. The preparation method comprises the following steps: separately preparing A component and B component and when using, mixing A component and B component in a weight ratio of 4:1 evenly to obtain the underwater solventless epoxy anti-corrosive coating. The invention has simple process, strong product adhesion, high mechanical strength and corrosion resistance; the coating can be especially used to coat members in water at a low temperature, has fast curing rate and good flexibility of coating film, and is hard to peel, thus being applicable to the protection of steel structures such as gates of hydroelectric power stations, sediment bottom sluices and the like and concrete structures.