The structures and energies of As-n (n = 2-8) neutrals, anions, and cations have been systematically investigated by means of the G3 schemes. The electron affinities, ionization potentials, binding energies, and several dissociation energies have been calculated and compared with limited experimental values. The results revealed that the potential surfaces of neutral As-n clusters are very shallow, and two types of structural patterns compete with each other for the ground-state structure of As-n with n >= 6. One type is derived from the benzvalene form of As-6, and another is derived from the trigonal prism of As-6. The previous photoelectron spectrum (taken from J. Chem. Phys. 1998, 109, 10727) for As-3 has been reassigned in light of the G3 results. The experimental electron affinities of As3 were measured to be 1.81 eV, not 1.45 eV. We inferred from the conclusion of G3 and density functional theory that the experimental electron affinities of 1.7 and 3.51 eV for As-5 are unreliable. The reliable electron affinities were predicted to be 0.83 eV for As-2, 1.80 eV for As-3, 0.54 eV for As-4, 3.01 eV for As-5, 2.08 eV for As-6, 2.93 eV for As-7, and 2.02 eV for As-8. The G3 ionization potentials were calculated to be 9.87 eV for As-2, 7.33 eV for As-3, 8.65 eV for As-4, 6.68 eV for As-5, 7.97 eV for As-6, 6.58 eV for As-7, and 7.65 eV for As-8. The binding energies per atom were evaluated to be 1.99 eV for As-2, 2.01 eV for As-3, 2.61 eV for As-4, 2.39 eV for As-5, 2.51 eV for As-6, 2.55 eV for As-7, and 2.67 eV for As-8. These theoretical values of As2, As3, and As4 are in excellent agreement with those of experimental results. Several dissociation energies were carried out to examine relative stabilities. This characterized the even-numbered clusters as more stable than the odd-numbered species.