Lithium-selenium batteries have emerged as a promising alternative to lithium-sulfur batteries due to their high electrical conductivity and comparable volume capacity. However, challenges such as the shuttle effect of polyselenides and high-volume fluctuations hinder their practical implementation. To address these issues, we propose synthesizing Fe-CNT/TiO2 catalyst through high-temperature sintering of an amalgamated nanoarchitecture of carbon nanotubes decorated metal–organic framework (MOF) and MXene, optimized for efficient selenium hosting, leveraging the distinctive physicochemical properties. The catalytic features inherent in the porous Se@Fe-CNT/TiO2 nanoarchitecture were instrumental in promoting efficient ion and electron transport, and lithium-polyselenide kinetics, while its inherent porosity could play a crucial role in inhibiting electrode stress during cycling. This nanoarchitecture exhibits remarkable battery performance, retaining 99.7% of theoretical capacity after 425 cycles at 0.5 C rate and demonstrating 95.8% capacity retention after 2000 cycles at 1 C rate, with ∼100% Coulombic efficiency. Additionally, the Se@Fe-CNT/TiO2 electrode exhibited an impressive recovery of 297.5 mAh/g (97.9%) capacity after undergoing 450 cycles at a charging rate of 10 C and a discharging rate of 1 C. This synergistic integration of MOF- and MXene-derived materials unveils new possibilities for high-performance and durable LSeBs, thus advancing electrochemical energy storage systems.