Although transition metal carbides/carbonitrides (MXenes) exhibit immense potential for electromagnetic wave (EMW) absorption, their absorbing ability is hindered by facile stacking and high permittivity. Layer stacking and geometric structures are expected to significantly affect the conductivity and permittivity of MXenes. However, it is still a formidable task to simultaneously regulate layer stacking and microstructure of MXenes to realize high‐performance EMW absorption. Herein, a simple and viable strategy using electrostatic adsorption is developed to integrate 2D Ti3C2Tx MXene nanosheets into 3D hollow bowl‐like structures with tunable layer stacking thickness. Density functional theory calculations indicate an increase in the density of states of the d orbital from the Ti atom near the Fermi level and the generation of additional electrical dipoles in the MXene nanosheets constituting the bowl walls upon reducing the layer stacking thickness. The hollow MXene bowls exhibit a minimum reflection loss (RLmin) of −53.8 dB at 1.8 mm. The specific absorbing performance, defined as RLmin (dB)/thickness (mm)/filler loading (wt%), exceeds 598 dB mm−1, far surpassing that of the most current MXene and bowl‐like materials reported in the literature. This work can guide future exploration on designing high‐performance MXenes with “lightweight” and “thinness” characteristics for superior EMW absorption. A simple and viable strategy using electrostatic adsorption is developed to integrate 2D Ti3C2Tx MXene nanosheets into 3D hollow bowl‐like structures with tunable layer stacking thickness. The layer stacking and geometric structures of the MXenes are simultaneously regulated to realize high‐performance electromagnetic wave absorption due to improved Ti vacancies, lattice distortions, degree of aggregation/stacking, and hollow structure.