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We report a joint experimental and theoretical study on the stability and reactivity of Bi n + (n = 5-33) clusters. The alternating odd-even effect on the reaction rates of Bi n + clusters with NO is observed, and Bi 7 + finds the most inertness. First-principles calculation results reveal that the lowest energy structures of Bi 6-9+ exhibit quasi-spherical geometry pertaining to the jellium shell model; however, the Bi n + (n � 10) clusters adopt assembly structures. The prominent stability of Bi 7+ is associated with its highly symmetric structure and superatomic states with a magic number of 34e closed shell. For the first time, we demonstrate that the unique s-p nonhybrid feature in bismuth rationalizes the stability of Bi 6-9+ clusters within the jellium model, by filling the 6s electrons into the superatomic orbitals (forming "sband"). Interestingly, the stability of 18e "s-band" coincides with the compact structure for Bi n + at n � 9 but assembly structures for n � 10, showing an accommodation of the s electrons to the geometric structure. The atomic p-orbitals also allow to form superatomic orbitals at higher energy levels, contributing to the preferable structures of tridentate binding units. We illustrate the s-p nonhybrid nature accommodates the structure and superatomic states of bismuth clusters.