As the sophistication and sensitivity of chemical instrumentation increase, so does the number of applications. Correspondingly, new questions and opportunities for systems previously studied also arise. As with most plants, the emission of volatiles from agricultural products is complex and varies among commodities. Volatiles are indicative of characteristics such as food quality, cultivar type, phenological stage, and biotic and abiotic stressors; thus, their systematic and accurate evaluation is important. Early volatile analyses entailed removal of the sample matrix in question, transport to the laboratory, and subsequent investigation. More recently, scientists are moving the laboratory to the field to obtain realistic emission patterns of the sample in its natural environment. This perspective proposes that a methodical and collaborative approach to the complex relationship between volatiles and agricultural commodities and their various phenological stages, oxidative degradation products, and fungal contamination is needed in order to fully comprehend the sample and associated relationships as a whole. These methodical approaches should incorporate both in situ and ex situ investigations of the sample. Ultimately, there exists an opportunity for development of methodologies that integrate both laboratory- and field-based collection of volatiles to explore and address the complex biological interactions of agricultural systems.