The invention relates to the technical field of exterior wall cold paints and discloses a super-hydrophobic self-cleaning colored grey cold wall paint and preparation and application methods thereof. The super-hydrophobic self-cleaning colored grey cold wall paint is prepared from the following components in percentages by mass: 30-50% of a styrene-acrylic emulsion, 10-30% of a water-based photoluminescent pigment, 3-20% of stearate, 5-10% of titanium dioxide, 0.5-2% of complementary color paste, 3-5% of an assistant and 10-30% of water, wherein the complementary color is cobalt-aluminum blue and Cromophtal orange; and the mass concentration of the complementary color paste is 20%. The super-hydrophobic self-cleaning colored grey cold wall paint is significant in super-hydrophobic self-cleaning effect, beautiful and practical, high solar reflectivity is effectively kept, and energy conservation and emission reduction are achieved.