MXenes and their nanostructures have been extensively studied as high-performance EMI shielding materials due to their excellent electrical conductivity and lightweight properties. Their performance has been known to surpass those of most conventional materials. As MXene structures are typically 2D laminates, there is much room to control the interlayer and interfacial architecture, which can lead to optimized and enhanced EMI shielding. Here, we introduce recently developed methods to modulate the interfacial architecture of MXene laminates. First, we will discuss the formation of extensive pore structures within MXene through a rapid foaming-like process. This allows a large enhancement of the total EMI SE and better understanding of the EMI shielding mechanism of MXene-based laminates. Second, we will briefly demonstrate a method to enhance the chemical and mechanical stability of MXene films through cross-linking, without degrading their original EMI shielding properties.