We begin this review with an introduction to pillar[n]arenes by showing the research history of macrocyclic compounds and the shape, chemical structure, host-guest properties, synthesis, and functionalization of pillar[n]arenes. We then present the modification of pillar[n]arenes on surfaces such as solid and porous surfaces for the creation of molecular-scale porous materials. We also highlight pillar[n]arene assemblies such as one-dimensional channels, twodimensional sheets, and three-dimensional vesicles, as well as the application of porous and soft-porous pillar[n]arene crystals for gas and organic vapor sorption materials. Finally, we discuss the advantages of using pillar[n]arenes for the synthesis of molecular-scale porous materials over other applications of pillar[n]arenes, as well as future perspectives in this exciting field.