Two (BE)8-[16]annulenes were prepared and fully characterized by experimental and quantum-chemical means (1, E = N; 2, E = O). The 1,8-naphthalenediyl-bridged diborane(6) 3 served as their common starting material, which was treated with [Al(NH3)6]Cl3 to form 1 (91% yield) or with 1,8-naphthalenediboronic acid anhydride to form 2 (93% yield). As a result, the heteroannulenes 1 and 2 are supported by four aromatic "clamps" and may also be viewed as NH- or O-bridged cyclic tetramers of BNB- or BOB-doped phenalenyls. X-ray crystallography on mono-, di-, and tetraadducts 2·thf, 2·py2, and 2·py4 showed that 2 is an oligotopic Lewis acid (thf/py: tetrahydrofuran/pyridine donor). The applicability of 2 also as a Lewis basic ligand in coordination chemistry was demonstrated by the synthesis of the mononuclear Ag+ complex [Ag(py)2(2·py4)]+ and the dinuclear Pb2+ complex 6. During the assembly of 6, the rearrangement of 2 led to the formation of two (BO)9-macrocycles linked by two BOB-phenalenyls to form a nanometer-sized cage with four negatively charged, tetracoordinated B atoms. Both 1 and 2 show several redox waves in the cathodic regions of the cyclic voltammograms. An in-depth assessment of the consequences of electron injection on the aromaticity of 1 and 2 was achieved by electronic structure calculations. 1 and 2 are proposed to exhibit aromatic switching capabilities in the [16]annulene motif.