Total reflection X-ray fluorescence (TXRF) analysis is conducted to determine trace elements in a sample solution, which is dropped onto a substrate and dried. Therefore, the form of the residue affects the quantitative results. The absorption of X-ray fluorescence (XRF) follows the Lambert-Beer law; the absorption effect of XRF in a thick residue (dotted-type residue) is stronger than that in a thin residue (film-type residue). The absorption effect is particularly remarkable during the determination of low-Z elements in a high-elemental concentration solution. In this study, we propose a new film-like-residue preparation process based on the freeze-drying method to obtain accurate TXRF results. The sample solution is dropped onto the substrate and inserted into a chamber. The chamber is cooled using liquid nitrogen; resultantly, an aliquot of the sample is frozen. The chamber is depressurized using a vacuum pump, and the freeze-dried residue is prepared by maintaining the chamber at room temperature. To evaluate the efficiency of the freeze-drying-based method for sample preparation for TXRF analysis, we prepare a multi-element solution containing high-elemental concentration components. For the residue prepared using the freeze-drying method, the relative standard deviations of the quantitative values and the minimum detection limits are improved because the absorption effect is weakened. The sample preparation process based on the freeze-drying method facilitates accurate TXRF analysis of high-elemental concentration solutions and can be applied for the analysis of trace elements in different types of solutions such as environmental water and wastewater.