Reaction of an N‐heterocyclic carbene (NHC)‐borenium ion with 9,10‐distyrylanthracene forms four B‐C bonds through two selective, tandem hydroboration—electrophilic C‐H borylations to yield an isolable, crystallographically characterizable polycyclic diborenium ion as its [NTf2]‐ salt (1). Dehydrogenation of 1 with TEMPO radical followed by acidic workup yields a 3,9‐diboraperylene as its corresponding borinic acid (2). This sequence can be performed in one pot to allow the facile, metal‐free conversion of an alkene to a small molecule containing a boron‐doped graphene substructure. Doubly boron‐doped perylene 2 exhibits visible range absorbance and fluorescence in chloroform solution (Φ = 0.63) and undergoes two reversible one electron reductions at moderate potentials of ‐1.30 and ‐1.64 eV vs. ferrocenium/ferrocene in DMSO. Despite sterically accessible boron centers and facile electrochemical reductions, compound 2 is air‐, moisture‐ and silica gel‐stable.