Plant-derived extracellular vesicles (P-EVs) have recently emerged as promising natural nanocarriers with considerable potential for sustainable crop protection and agricultural biotechnology. Once regarded as cellular byproducts, P-EVs are now recognized as key mediators of intercellular and interkingdom communication, transporting diverse bioactive cargos, including small RNAs (sRNAs), proteins, lipids, and metabolites. Increasing evidence demonstrates that P-EVs play critical roles in plant immunity by facilitating cross-kingdom RNA interference (RNAi), through which host-derived sRNAs are delivered to invading pathogens to suppress virulence-associated genes and enhance disease resistance. In this review, we summarize current advances in the understanding of P-EV biology, including their biogenesis, classification, cargo composition, and mechanisms of cargo sorting. We further discuss the roles of P-EVs in plant responses to pathogens, with particular emphasis on their involvement in plant–microbe interactions and EV-mediated cross-kingdom communication. Recent developments supporting the application of P-EVs as natural delivery platforms for RNA-based crop protection strategies, including host-induced gene silencing (HIGS) and spray-induced gene silencing (SIGS), are also highlighted. Finally, we examine the major challenges associated with P-EV isolation, characterization, large-scale production, and preservation, and outline future research directions required for their translation into practical agricultural applications. Collectively, P-EVs represent a promising and environmentally friendly platform for next-generation crop protection, offering new opportunities to reduce dependence on conventional agrochemicals while enhancing crop resilience and food security.