A newly developed laser desorption and laser postionization time-of-flight mass spectrometer (LD-LPI-TOFMS) for the direct microtrace determination of rare earth elements (REEs) in residues has been presented. Benefiting from spatially and temporally separated processes between desorption and ionization, LD-LPI-TOFMS plays a dual role in alleviating the barriers of deteriorating spectral resolution at high irradiance, serious matrix effects and elemental fractionation effects at low irradiance. Compared with the conventional laser desorption/ionization (LDI) method, this technique offers unambiguous full-elemental determination of 15 REEs with more uniform relative sensitivity coefficients (RSCs) ranging from 0.5 to 2.5 for all REEs investigated, satisfying the semiquantitative analysis criteria. More importantly, a highly sensitive analysis of REEs with very little consumption was achieved by getting the utmost out of desorbed neutral atoms instead of increasing the amount of the sample, resulting in outstanding relative and absolute limits of detection (LODs and ALODs) of ∼ng/mL and ∼femtogram. The results presented here indicate that LD-LPI-TOFMS offers great potential in microtrace determination for elements in solution samples with minor sample preparation.