Icing and frosting on transparent surfaces compromise visibility on various optical equipment and transparent infrastructures. It remains challenging to fabricate energy-saving coatings for harvesting solar energy while maintaining high transparency. Here, transparent, photothermic, and icephobic composite surfaces composed of photothermal nanomaterials and polyelectrolytes via layer-by-layer assembly are designed and constructed. The positively-charged polypyrrole nanoparticles and negatively-charged poly(acrylic acid) are assembled as exemplary materials via electrostatic attractions. The optically transparent photothermal coatings are successfully fabricated and exhibited photothermal capabilities and light-transmittance performance. Among the various coatings applied, the seven-bilayer coating can increase the temperature by 35 °C under 1.9-sun illumination, maintaining high transmittance (>60%) of visible light. With sunlight illumination at subzero temperatures (> -35 °C), the coatings show pronounced capabilities to inhibit freezing, melt accumulated frost, and decrease ice adhesion. Precisely, the icephobic surfaces remain free of frost at -35 °C as long as sunlight illumination is present; the accumulated frost melts rapidly within 300 s. The ice adhesion strength decreases to ≈0 kPa as the melted water acts as a lubricant. Furthermore, the negatively-charged graphene oxide and positively-charged poly(diallyldimethylammonium chloride) show their material diversity applicable in the coating fabrication.