The invention relates to a solvent-free epoxy coating for the inner wall of a petroleum storage tank and a preparation method. Solution A comprises E-51 epoxy resin, butyl glycidyl ether, KH-560 silane coupling agent, ALCOPHOR827 anti-corrosion auxiliary agent, BYK-085 flatting agent, Efka-722 defoamer, 400 mesh rutile type titanium white, 325 mesh baryte powder, 400 mesh talcum powder, carbon black and 881-B organic bentonite. Solution B comprises polyamide EU8235 epoxy hardener, dimethylbenzene and normal butanol. The weight percent of the solution A is 80% to 90%. The solvent-free epoxy coating is safe and environment friendly, the coating volume shrinkage is 1.15% to 1.5%, the pull-off adhesion is 16.5MPa to 20.0MPa, a chemical media resistance 90d paint film is in good condition, anda salt spray resistance 3000h paint film is in good condition. With the adoption of the solvent-free epoxy coating, corrosion of the storage tank can be greatly reduced, and the service life of the storage tank can be greatly prolonged.