Polyamines (PAs), which are aliphatic polycationic compounds with a low molecular weight, are found in all living organisms and play essential roles in plant–pathogen interactions. Putrescine, spermidine, and spermine, the most common PAs in nature, respond to and function differently in plants and pathogens during their interactions. While plants use certain PAs to enhance their immunity, pathogens exploit PAs to facilitate successful invasion. In this review, we compile recent studies on the roles of PAs in plant–pathogen interactions, providing a comprehensive overview of their roles in both plant defense and pathogen pathogenicity. A thorough understanding of the functions of PAs and conjugated PAs highlights their potential applications in fungicide development. The creation of new fungicides and compounds derived from PAs demonstrates their promising potential for further research and innovation in this field.