This study aims to analyse the thermal efficiency of wall elements with varying position-allocation-thickness of insulation, in the aspect of the optical properties of their external paint. A special focus has been placed on the role of solar reflectivity in wall coatings while taking into account the impact of the ambient environment at all cardinal points. In this light, the problem of urban environment warming must be addressed, while considering occupant reliance on air-conditioning. In the initial stage, the key research objective is to shed some light on the performance of analysed wall assemblies in terms of thermal sensitivity (decrement factor and time lag). On the other hand, at the targeting stage, our main intention is to demonstrate the eminence of solar heat-rejecting paints on the cooling power demand of wall arrangements. Furthermore, this work is extended to the assessment of the overall heating and cooling demands on an annual basis. A thermal-network model is developed within this framework to determine temperature variations and heat fluxes in the margins of the examined setups. The potential benefits of the suggested model are twofold. Accordingly, the findings of the numerical analyses reveal the configurations and operating conditions proving the optimal dynamic thermal parameters and energy demand. Numerical simulations indicate that an optimal cooling power capacity is noticeable for wall surfaces covered with solar heat-rejecting paints; cooling saving can exceed 90% for highly solar-reflective surfaces. However, when it comes to unveiling the global performability of ultra-white paints the overall improvement of conditions may vary radically; a reflective paint will probably not be sufficient to counterbalance both heating and cooling concerns. In terms of annual heat transmission loads, results exhibit an optimal solar absorptivity of 0.35 for north/east/west facing walls and 0.75 for south-oriented walls. Also, within the confines of our attention, by the increase of insulation level, the energy benefit can reach up to 40% per annum.