The energies, fine structure splittings, transition rates, and lifetimes of inner-shell excited sextet states 1s2s2p2nl, (n = 2–7; l = s, p, d) and 1s2p33p of the boron isoelectronic sequence (Z = 8–13) are investigated using the multi-configuration Rayleigh–Ritz variation method. The mass polarization effect and relativistic corrections are included by first-order perturbation theory. Configuration structures of the high-n inner-shell excited sextet series 6Se,o(m) and 6Pe,o(m) (m = 1–5) of boron-like Na6+ ion are assigned. The wavelengths and transition rates of electric-dipole transitions between 6Pe(m) and 6Po(m) (m = 1–5) states are calculated. The quantum electrodynamics (QED) effects and higher order relativistic corrections are also considered to obtain more accurate transition wavelengths. The predicted transition wavelengths agree well with the available theoretical and experimental data. The lifetimes for the inner-shell excited sextet states 6Pe(m) (m = 1–5) are also reported and discussed with the increase of nuclear charge number, Z. These theoretical data are useful for the identification of spectral lines in experiments and the design of XUV and soft X-ray lasers.