Plants are at the trophic base of most ecosystems, embedded in a rich network of ecological interactions in which they evolved. While their limited range and speed of motion precludes animal-typical behavior, plants are accomplished chemists, producing thousands of specialized metabolites which may function to convey information, or even to manipulate the physiology of other organisms. Plants’ complex interactions and their underlying mechanisms are typically dissected within the controlled environments of growth chambers and glasshouses, but doing so introduces conditions alien to plants evolved in natural environments, such as being pot-bound, and receiving artificial light with a spectrum very different from sunlight. The mechanistic understanding gained from a reductionist approach provides the tools required to query and manipulate plant interactions in real-world settings. The few tests conducted in natural ecosystems and agricultural fields have highlighted the limitations of studying plant interactions only in artificial environments. Here, we focus on three examples of known or hypothesized chemical mediators of plants’ interactions: the volatile phytohormone ethylene (ET), more complex plant volatile blends, and as-yet-unknown mediators transferred by common mycorrhizal networks (CMNs). We highlight how mechanistic knowledge has advanced research in all three areas, and the critical importance of field work if we are to put our understanding of chemical ecology on rigorous experimental and theoretical footing, and demonstrate function.