Laser-induced breakdown spectroscopy (LIBS), a fast and real-time tool for elemental analysis, has attracted great attention due to its broad applications in trace detection, geological environment monitoring, and other fields. The sample surface is one of the key environmental factors that affect the generation and characteristics of plasma. In this work, a 1 064 nm-laser beam with a pulse width of 8 ns is used to produce plasma in ambient air and comparatively investigate the emission spectra of a series of natural rock samples under non-flat and flat samples surfaces. Based on the laser-supported detonation wave model, the influence of non-flat sample surface on spectral characteristics of laser-induced plasmais discussed. For time-integrated spectra, the results show that the spectral intensities of the atomic lines of the non-flat sample are reduced by nearly 70% compared to those of the flat sample. This indicates that the negative effect of the non-flat sample surface on the LIBS cannot be ignored. According to the signal intensity of the spectral lines, Fe Ⅰ 404.58 nm and Fe Ⅰ 438.35 nm from limonite sample under different laser energies, the variation of their peak intensities and reduction factor with the change of laser energy were studied under the conditions of flat and non-flat sample surfaces. It is found that the spectral intensity under the condition of the non-flat sample surface is lower than that under the condition of the flat sample surface. It is worth noting that the reduction factor of spectral intensity first decreases gradually with laser energy, reaches the minimum value at 33 mJ, and then increases with the further increase of laser energy. Further observations show that laser-plasma with lower electron density is generated on the non-flat sample surface, and the ratio of the electron density of the non-flat sample to that of the flat sample reaches its minimum at the laser energy of 33 mJ, which is consistent with the changing trend of reduction factor with laser energy. This mainly arises because a thinner energy absorption region in laser-plasma is formed due to the large laser incident angle on the non-flat sample surface, thereby increasing the laser energy threshold corresponding to the plasma shielding. Moreover, it is found that the sample surface and the laser energy have little effect on the plasma temperature.