The eight-coordinate early transition metal polyarsenic complexes, MAs83- (M = V, Nb, Ta), MAs82- (M Cr, Mo, W), and MAs8- (M = Mn, Tc, Re), have been studied using density functional theory (DFT). The geometry optimizations of these complexes indicate that in the most stable structures the transition metal atoms are trapped in a crownlike cavity: consisting of a zigzag eight-membered ring of As-8 cluster. The scalar-relativistic effects and spin-orbit coupling effects on the electronic structures and energy levels were taken into account, The stabilities of gas-phase MAs8n- ions and bonding between the As-8 ring and early transition metals are discussed an the basis of population analysis, atomization energies, and decomposition reaction energies. All these complex ions are found to be diamagnetic with notable HOMO-LUMO energy gaps. The vibrational frequencies and infrared absorption intensities of the MAs8n- series are predicted theoretically. Brief theoretical calculations of the similar MoA(8)(2-) pnictide ions indicate that the analogous P, Sb, and even Bi complexes are likely to be stable, whereas the crownlike MoN82- is not a stable complex.