Аннотация:The anomalous behavior of laser plume temperature was observed in this work after evaporating annealed ceramics. This circumstance allows sorting annealed and non-annealed lithium ferrites which contain the same phase of LiFe 5O8 by LIBS. The correlation between both optoacoustic signal and emission signal of matrix element and ablated volume is studied as well as. It was found linear dependence of optoacoustic signal on crater volume, but iron emission depended on volume non-linearly. Therefore, optoacoustic is preferable for correction of experimental condition changes during analysis of those samples by methods with laser ablation.