Pesticide residues in fruits and vegetables pose a serious threat to food safety. Traditional detection methods have defects such as complex operation, high cost, and long detection time. Therefore, it is of great significance to develop rapid, non-destructive, and efficient detection technologies and equipment. In recent years, the combination of spectroscopic techniques and imaging technologies with machine learning algorithms has developed rapidly, providing a new attempt to solve this problem. This review focuses on the research progress of the combination of spectroscopic techniques (near-infrared spectroscopy (NIRS), hyperspectral imaging technology (HSI), surface-enhanced Raman scattering (SERS), laser-induced breakdown spectroscopy (LIBS), and imaging techniques (visible light (VIS) imaging, NIRS imaging, HSI technology, terahertz imaging) with machine learning algorithms in the detection of pesticide residues in fruits and vegetables. It also explores the huge challenges faced by the application of spectroscopic and imaging technologies combined with machine learning algorithms in the intelligent perception of pesticide residues in fruits and vegetables: the performance of machine learning models requires further enhancement, the fusion of imaging and spectral data presents technical difficulties, and the commercialization of hardware devices remains underdeveloped. This review has proposed an innovative method that integrates spectral and image data, enhancing the accuracy of pesticide residue detection through the construction of interpretable machine learning algorithms, and providing support for the intelligent sensing and analysis of agricultural and food products.