Aromaticity is one of the most intriguing concepts in organic chemistry. Simple and extended benzenoid aromatic systems have been very well established in undergraduate textbooks, and there are also mentions of non-benzenoid aromatic structures such as cyclopropenium, cyclopentadienide and cycloheptatrienylium (tropylium) ions. However, the structural relationship and the comparison of stabilization energy of such aromatic ions to benzene ring have been rarely studied and remained an underexplored area of advanced organic chemistry research. To contribute some insights into this topic, we focused on the chemical transformation, namely a ring contraction reaction, of the tropylium ion to benzene ring in this work. With an approach combining computational studies with experimental reactions, we also aim to turn this transformation into a synthetically useful tool. Indeed, this work led to the development of a new synthetic protocol, which involved an oxidative ring-contraction of tropylium ion, to formally introduce the phenyl ring onto a range of organic structures. Furthermore, the homoaromatic cycloheptatrienyl precursors of tropylium salts used in these reactions can also be rearranged to valuable benzhydryl or benzyl halides, enriching the synthetic utility of this ring-contraction protocol.