Microorganisms are found everywhere, and they are closely associated with plants. Because the establishment of any plant–microbe association involves chemical communication, understanding crosstalk processes is fundamental to defining the type of relationship. Although several metabolites from plants and microbes have been fully characterized, their roles in the chemical interplay between these partners are not well understood in most cases, and they require further investigation. In this review, we describe different plant–microbe associations from colonization to microbial establishment processes in plants along with future prospects, including agricultural benefits.