This study explores the enhancement of low-frequency microwave absorption in MXene-based materials through structural polarization modulation. MXene, a two-dimensional carbon-based material, is known for its excellent electromagnetic wave absorption capabilities in mid- and high-frequency ranges but faces challenges in low-frequency absorption due to limited control over polarization response mechanisms. The research proposes a novel approach to improve absorption efficiency in aligned three-dimensional (3D) MXene/CNF (cellulose nanofibers) cavities by modifying polarization properties and manipulating resonance response. This method results in a significant shift of the main absorption region from the X-band to the S-band, achieving a reflection loss (RL) value of −47.9 dB in the low-frequency range. The study reveals that oriented electromagnetic coupling plays a crucial role in influencing electromagnetic response and microwave absorption properties. The findings provide a generic strategy for low-frequency tuned absorption without the need for magnetic elements, making MXene-based materials lightweight, eco-friendly, and suitable for applications in 5G and stealth defense technologies.This study explores the enhancement of low-frequency microwave absorption in MXene-based materials through structural polarization modulation. MXene, a two-dimensional carbon-based material, is known for its excellent electromagnetic wave absorption capabilities in mid- and high-frequency ranges but faces challenges in low-frequency absorption due to limited control over polarization response mechanisms. The research proposes a novel approach to improve absorption efficiency in aligned three-dimensional (3D) MXene/CNF (cellulose nanofibers) cavities by modifying polarization properties and manipulating resonance response. This method results in a significant shift of the main absorption region from the X-band to the S-band, achieving a reflection loss (RL) value of −47.9 dB in the low-frequency range. The study reveals that oriented electromagnetic coupling plays a crucial role in influencing electromagnetic response and microwave absorption properties. The findings provide a generic strategy for low-frequency tuned absorption without the need for magnetic elements, making MXene-based materials lightweight, eco-friendly, and suitable for applications in 5G and stealth defense technologies.