For molecules containing the fourth-period element arsenic, we test (i, ii) the accuracy of all-electron (AE) basis sets from the def2-xZVP and ma-xZVP series (where xZ is S, TZ, or QZ), (iii) the accuracy of the 6-311G series of AE basis sets with additional polarization and diffuse functions, and (iv) the performance of effective core potentials (ECPs). The first set of tests involves basis-set convergence studies with eleven density functionals for five cases: equilibrium dissociation energy (De) of As2, vertical ionization potential (VIP) of As2, IP of As, acid dissociation of H3AsO4, and De of FeAs. A second set of tests involves the same kinds of basis-set convergence studies for the VIP and D e values of As3 and As4 clusters. Both relativistic and nonrelativistic calculations are considered, including in each case both AE calculations and calculations with ECPs. Convergence and accuracy are assessed by comparing to relativistic AE calculations with the cc-pV5Z-DK or ma-cc-pV5Z-DK basis and to nonrelativistic AE calculations with the cc-pV5Z or ma-cc-pV5Z basis. The primary objective of this study is to evaluate the abilities of ECPs with both their recommended basis sets and other basis sets to reproduce the results of all-electron relativistic calculations. The performance of the def2 and ma series basis sets is consistent with their sizes, and quadruple-ζ basis sets are the best. The def2-TZVP basis set performs better than most of the 6-311G series basis sets, which are the most commonly used basis sets in the previous studies of arsenic compounds. However, relativistic def2-TZVP calculations are not recommended. The large-core ECPs, which are the only available ECPs for arsenic in the popular Gaussian program, have average errors of 9-12 kcal/mol for the arsenic systems studied; therefore, these ECPs are not recommended. The triple-ζ small-core relativistic ECP (RECP) basis set cc-pVTZ-PP is found to have performance better than that of the def2-TZVP basis set, and it is highly recommended for arsenic-containing systems. The double-ζ RECP basis set ma-sc-SVP is recommended for large arsenic systems for which the def2-TZVP and cc-pVTZ-PP basis sets are unaffordable, if a basis-set error of ∼2 kcal/mol can be tolerated.