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Because of their interesting structures and bonding and potentials as motifs for new nanomaterials, size-selected boron clusters have received tremendous interest in recent years. In particular, boron cluster anions (B n − ) have allowed systematic joint photoelectron spectroscopy and theoretical studies, revealing predominantly two-dimensional structures. The discovery of the planar B 36 cluster with a central hexagonal vacancy provided the first experimental evidence of the viability of 2D borons, giving rise to the concept of borophene. The finding of the B 40 cage cluster unveiled the existence of fullerene-like boron clusters (borospherenes). Metal-doping can significantly extend the structural and bonding repertoire of boron clusters. Main-group metals interact with boron through s/p orbitals, resulting in either half-sandwich-type structures or substitutional structures. Transition metals are more versatile in bonding with boron, forming a variety of structures including half-sandwich structures, metal-centered boron rings, and metal-centered boron drums. Transition metal atoms have also been found to be able to be doped into the plane of 2D boron clusters, suggesting the possibility of metalloborophenes. Early studies of di-metal-doped boron clusters focused on gold, revealing ladder-like boron structures with terminal gold atoms. Recent observations of highly symmetric Ta 2 B 6 − and Ln 2 B n − ( n = 7–9) clusters have established a family of inverse sandwich structures with monocyclic boron rings stabilized by two metal atoms. The study of size-selected boron and doped-boron clusters is a burgeoning field of research. Further investigations will continue to reveal more interesting structures and novel chemical bonding, paving the foundation for new boron-based chemical compounds and nanomaterials.