The literature reports two methods for the production of cool cement-based materials, namely, application of pigments into the cement mix or as a coating. However, no comparative analysis of those methods has been conducted yet. This study investigates the effect of the white pigments’ application mode on the optical properties of cement-based materials. Spectral reflectance and color coordinates were measured on 60 × 60 × 11 mm mortar samples with titanium dioxide rutile and a commercial white pigment added to the mortar (1, 5, and 10% of the cement weight) or applied as a coating (1, 5, 10, and 20% of pigment concentration on acrylic white paint). Solar reflectance for coating application was higher than mortar one. For a similar amount of pigment (0.62 g), the coating application showed solar reflectance 0.238 higher than the one of the mortar applications for titanium dioxide and 0.209 for pigment white 6. Additionally, the color coordinate L* (lightness-darkness) for coating application is higher than for mortar application. It can be concluded that the method of application of white pigments affects reflectance and color appearance of cement-based materials, whereas their application as a coating resulted in higher solar reflectance and lightness in comparison to their addition into the cement mix, since the pigment is entirely deposited over the sample’s surface for coating application. Future studies should investigate the effects of a natural weathering campaign and explore other pigments towards the development of guidelines for the selection and production of cool and supercool materials.