Single-walled carbon nanotubes (SWNTs), as one of the most promising one-dimension nanomaterials due to its unique structure, peculiar chemical, mechanical, thermal, and electronic properties, have long been considered as an important building block to construct ordered alignments. Vertically aligned SWNTs (v-SWNTs) have been successfully prepared by using direct growth and chemical assembly strategies. In this review, we focus explicitly on the v-SWNTs fabricated via chemical assembly strategy. We provide the readers with a full and systematic summary covering the advances in all aspects of this area, including various approaches for the preparation of v-SWNTs using chemical assembly techniques, characterization, assembly kinetics, and electrochemical properties of v-SWNTs. We also review the applications of v-SWNTs in electrochemical and bioelectrochemical sensors, photoelectric conversion, and scanning probe microscopy.