The anionic boron peri-bridged naphthalene derivative, namely dimesityl-1,8-naphthalenediylborate (1), undergoes a hydrolysis reaction to afford dimesityl-1-naphthylborane (2) whose structure has been determined. Upon standing at room temperature in toluene for an extended period of time, 1 undergoes a ring expansion reaction to afford 8,10,11a-trimethyl-7-mesityl-11aH-7-boratabenzo[de]anthracene (3). As shown by its crystal structure, compound 3 constitutes a rare example of a borataalkene and features a carbon–boron double bond of 1.475(6) Å incorporated in a conjugated hexa-1-boratatriene system. The reaction of 1 with 9-chloro-9-borafluorene and 5-bromo-10,11-dihydrodibenzo[b,f]borepin results in the formation of diboranes 4 and 5 which bear two different boryl moieties at the peri-positions of naphthalene. These diboranes have been characterized by multinuclear NMR spectroscopy and X-ray single crystal analysis. The boron center of the borafluorenyl moiety is π-coordinated to the ipso-carbon of a mesityl group with which it forms a contact of 2.730(3) Å. The cyclic voltammogram of 2 in THF shows a quasi-reversible reduction wave at E_1/2 −2.41 V (vs. Fc/Fc⁺) corresponding to the formation of the radical anion. In the case of diboranes 4, 5 and 1-(dimesitylboryl)-8-(diphenylboryl)naphthalene (6), two distinct waves are observed at E_1/2 −2.14 and −2.56 V for 4, E_1/2 −2.26 and −2.78 V for 5, and E_1/2 −2.41 and −2.84 V for 6. The first reduction wave most likely indicates the formation of a radical anion in which the unpaired electron is σ-delocalized over the two boron centers.