The invention discloses composite heat-insulating paint for exterior walls and a preparation method of the composite heat-insulating paint. The composite heat-insulating paint is prepared from purified water, an inorganic dispersing agent, a defoaming agent, texanol ester alcohol, rutile titanium dioxide, nano-titanium silicate microporous powder, porous expansible microspheres, infrared reflection nano-pigment, a self-crosslinking fluorocarbon emulsion, a photocured elastic emulsion, a macromolecular porous polymer, a nano-zirconium dioxide dispersing agent, a nano-titania colloid, a nano-silica solution, a nano-silver antibacterial agent and a PU thickening agent. The heat-insulating paint has efficient heat radiation reflection performance, good heat insulation and self-cleanness, lasting heat, good decorative performance, wide applicability and great environment friendliness, and a coating is long in service life.