This study reports for the first time, the thermoelectric (TE) performance of continuous p- and n-type carbon nanotube fiber (CNTF) filaments integrated within a sustainable, fine-grained geopolymer (GP) based concrete matrix for the complete replacement of cement with supplementary cementitious materials towards CO₂ emissions reduction policy. Moreover, CNTF as CO₂ negative, conductive, durable and lightweight material could multidimensionally contribute on the achievement of sustainability goals. Herein, pristine CNTF filaments were molecularly modified with p- and n-type aqueous-based dopants in order to stably tune their intrinsic semi-conducting properties via a facile and scalable dip-coating process. The achieved Seebeck coefficient values of the optimized p- and n-type CNTF were +45.2 μV/K and −38.4 μV/K, respectively. Thereafter, the p- and n-type CNTF filaments were employed as pillar-like thermoelectric elements incorporated within a GP mixture for the assembly of a structural thermoelectric generator (TEG) device. The obtained TEG-enabled GP-based concrete demonstrator comprising of 8 p-n serially interconnected junctions is capable of generating a power output of 0.3 μW at an applied through-thickness temperature gradient (ΔT) of 50 Κ. Subsequently, the experimental work was validated using coupled field of TE simulations. Self-powered infrastructures are forecasted to efficiently benefit from available ΔT on large-scale upon their operational lifetime, further promoting future net-zero energy consumption concepts.