The structures and relative stability of the maximum-spin n+1Aun and nAu+n (n = 2–8) clusters have been determined by density-functional theory. The structure optimizations and vibrational frequency analysis are performed with the gradient-corrections of Perdew along with his 1981 local correlation functional, combined with SBKJC effective core potential, augmented in the valence basis set by a set of f functions. We predicted the existence of a number of previously unknown isomers. The energetic and electronic properties of the small high-spin gold clusters are strongly dependent on sizes. The high-spin clusters tend to holding three-dimensional geometry rather than planar form preferred in low-spin situations. In whole high-spin Aun (n = 2–8) neutral and cationic species, 5Au4, 2Au+2, and 4Au+4 are predicted to be of high stability, which can be explained by valence bond theory. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [ABSTRACT FROM AUTHOR]