Abstract: Pesticide residues present significant threats to food safety and public health, necessitating the development of rapid, sensitive, and portable detection methods. Surface-enhanced Raman spectroscopy (SERS) has demonstrated great potential in the field of pesticide residue detection due to its advantages of ultrahigh sensitivity, molecular fingerprint capability, and minimal sample pretreatment requirements. Silver nanoparticles (AgNPs), the most representative SERS-active materials, exhibit morphology-dependent electromagnetic enhancement effects. Variations in exposed crystal facets, sharp-tip structures, and “hot spot” configurations strongly influence their enhancement mechanisms and sensing performance. This review systematically summarizes the synthesis strategies and SERS enhancement mechanisms of AgNPs with typical morphologies, along with their applications in detecting different classes of pesticide residues. The relationship between nanostructured characteristics and suitability for detection of pesticides is discussed. Finally, future perspectives on the development of SERS for pesticide residue analysis are prospected, aiming to provide valuable insights for developing advanced SERS substrates in food safety monitoring.