Abstract: Neonicotinoid pesticides, characterized by high efficiency, broad-spectrum application, low toxicity, and remarkable selectivity, are now the most widely used insecticides worldwide. Nonetheless, these pesticides pose potential risks to the human nervous and reproductive systems through exposure via drinking water, food, and inhalation. This paper comprehensively summarizes the types, sample preparation techniques, and value assignment methodologies for certified reference materials (CRMs) of neonicotinoid pesticides, crucial for ensuring accurate, comparable, and traceable quantitative detection results. In China, CRMs primarily consist of purity and solution reference materials, chiefly incorporating acetamiprid and imidacloprid. However, there is a significant shortage of matrix reference materials. Purity CRMs are typically prepared by purifying commercially available materials, and their values are primarily assigned using mass balance methods and differential scanning calorimetry. Conversely, international institutes have developed a plethora of matrix CRMs for neonicotinoid pesticides, containing various analytes. These matrix samples are prepared by spiking blank or positive samples with the expected concentration of analytes and are subsequently quantified using liquid chromatography isotope dilution mass spectrometry (LC-ID-MS). The development of neonicotinoid pesticide CRMs in China lacks balance both in type and structure. Hence, the development of multi-component and multi-level matrix CRMs for neonicotinoid pesticides needs to be accelerated to improve the quantitative traceability system and meet the growing demand for extensive testing.