The global increase in energy needs and environmental awareness for a more efficient energy use have boosted building rehabilitation to decrease energy consumption. The installation of solar control films (SCFs) in buildings with large glazing façades makes it possible to reduce excessive solar gains through the glazing. The main purpose of the work is to assess, with field experimental data, the thermal and luminous performances of double-glazing units with SCFs installed in office rooms, in Lisbon. An experimental campaign was carried out simultaneously in three adjacent offices: one with a highly reflective SCF (external installation), one with a reflective SCF (internal installation) and one without an SCF. The exterior SCF showed the best thermal performance with reductions in the peak indoor air temperature of up to 6.9 and 2.3 °C during the representative days of the heating and cooling periods, respectively, increasing thermal comfort mainly during the cooling period. The interior SCF had a poorer thermal performance since it contributed to solar radiation absorption that is then emitted as heat into the indoor environment, increasing the greenhouse effect of the office. The presence of SCFs reduced the indoor illuminance levels, having a positive impact on thermal comfort and glare reduction in the cooling period.