Alkali-activated materials, also known as geopolymers, are considered promising assets in the sustainable materials industry. Given the excellent properties in terms of thermal stability and low thermal conductivity, geopolymer-based matrices can effectively substitute cementitious binders in the preparation of passive fire protection (PFP) systems. The present study aims at evaluating the environmental footprint of a newly proposed geopolymer-based fireproofing material. The results are compared to a reference commercial lightweight cement-based coating with equal PFP performance. The boundaries of the system assessed were based on a cradle-to-grave life cycle. A preliminary scale-up of the laboratory protocol allowed the evaluation of the industrial production of the geopolymer-based PFP mix. An ancillary life cycle analysis was performed, comparing the environmental footprint of a geopolymer-based concrete block to the relevant literature studies for the same system in order to validate the approach of the present study. The functional unit of the main study was defined, taking into account the material performance in terms of resistance to heat exposure, allowing a functional comparison with lightweight cement-based PFP. The impact assessment phase used the CML-IA methodology as a characterization method. The ancillary LCA confirmed the alignment of the assumptions of the current study with previous analyses. The analyzed geopolymer-based fireproofing material exhibited a life cycle impact which is 27% lower than the lightweight concrete reference in terms of the global warming indicator, mainly thanks to the avoided CO2 emissions from the clinker process in cement manufacturing. Therefore, the greenhouse gas reduction described in previous studies on geopolymer application as a strong environmental advantage of the geopolymer technologies is also confirmed in this case. However, the other considered impact categories, such as resource depletion, acidification, eutrophication, and human toxicity, resulted in indicator values higher than the reference, as a consequence of the energy-intensive production process for the alkali activators (in particular, sodium silicate). Though the reduction of greenhouse gas emissions is confirmed, the overall sustainability of geopolymers for PFP applications is hindered by the relevant environmental footprint of the sodium silicate production process. However, a substantial reduction of the impacts could be achieved by selecting the production process of sodium silicate which takes advantage of renewable energy supplies (e.g., hydrothermal route) or by reducing the amount of sodium silicate in the geopolymer recipe in favor of waste-based alkali activators.