This paper reports a systematic study on the doping of two potassium atoms in small-sized neutral boron clusters. The CALYPSO software in conjunction with DFT was used to anticipate the low-energy structures, optimize their geometry, and adjust their energies. With increasing size, the structural development of the K2Bn (n=1–12) clusters was revealed, and we discovered that the majority of their ground-state structural isomers structurally inherited well from the corresponding ground-state isomers of pure B clusters. A fresh fnding was made after confrming the NPA (natural population analysis) of the low-lying K2Bn (n=1–12): every doped K atom in the structure has a positive charge. According to relative stability analysis, the most stable K2B8 cluster within the parameters of our investigation has a HOMO–LUMO gap of 3.31 eV. Strong interactions between K-4s and B-2P AO were also discovered through an additional examination of the molecular orbitals and bonds of K2B8 clusters. These interactions may be the primary cause of K2B8's exceptional stability. We hope that our research will be useful in the future for synthesizing and using doped boron-based nanomaterials.