A simple strategy was used to prepare functional two-dimensional materials via the combination of pillar[5]arene (P5) and MXene. The electrochemical results of MXene-P5 exhibit high supramolecular recognition, enrichment capability, and high electrochemical response toward dye molecules, which are probably due to the synergetic effects from high conductivity, high surface area, and host–guest recognition. This study provides a promising electrochemical sensing platform based on different kinds of pillararenes.