The lattice Boltzmann method (LBM), which was originally designed for near-incompressible Navier–Stokes flows, has been extended to rarefied gas flows with high-order quadrature in recent years. Although the ability of the high-order LBM to capture rarefaction effects has been demonstrated by many authors, its accuracy and efficiency are often undermined by numerical dissipation introduced by the off-lattice abscissas in Gauss–Hermite quadrature. Here, using the spontaneous Rayleigh–Brillouin scattering problem as the benchmark, we assess the accuracy and efficiency of the high-order LBM with on-lattice quadrature rules up to 39th order. The numerical error comprises two parts, one due to the rarefaction effect and the other due to temporal-spatial discretization, and we find that the former depends not only on the number of discrete velocities, but also on their distribution in velocity space. With a quadrature of 29th order, the error between the LBM and the discrete velocity method is found to be below 1 % up to $Kn=2.0$. Compared with a finite-volume Bhatnagar–Gross–Krook solver using Gauss–Hermite quadrature, the on-lattice LBM has a numerical dissipation several orders of magnitude lower, and achieves the same accuracy with fewer discrete velocities.