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.