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Precast concrete sandwich panels (PCSPs) are known for their good thermal, acoustic and structural properties. Severe environmental demands can be met by PCSPs due to their use of highly thermally insulating materials and non-metallic connectors. One of the main issues limiting the wider use of sandwich walls in construction is their unknown fire resistance. Furthermore, the actual behaviour of connectors and insulation in fire in terms of their mechanical performance and their impact on fire spread and the fire resistance of walls is not fully understood. This paper presents an experimental investigation on the structural and thermal behaviour of PCSPs with mineral-wool insulation and glass-fiber-reinforced polymeric bar connectors coupling two concrete wythes. Three full-size walls were tested following the REI certification test procedure for fire walls under fire and vertical eccentric and post-fire mechanical impact load. The three test configurations were adopted for the assessment of the connectors’ fire behaviour and its impact on the general fire resistance of the walls. All the specimens met the REI 120-M criteria. The connectors did not contribute to the fire’s spread and the integrity of the walls was maintained throughout the testing time. This was also confirmed in the most unfavourable test configuration, in which some of the connectors in the inner area of the wall were significantly damaged, and yet the structural connection of the concrete wythes was maintained. The walls experienced heavy heat-induced thermal bowing. The significant contribution of connectors to the stiffness of the wall during fire was observed and discussed. Full article