Plants produce and utilize a great diversity of chemicals for a variety of physiological and ecological purposes. Many of these chemicals defend plants against herbivores, pathogens and competitors. The location of these chemicals varies within the plant, some are located entirely within plant tissues, others exist in the air- (or water-) space around plants, and still others are secreted onto plant surfaces as exudates. I argue herein that the location of a given defensive chemical has profound implications for its ecological function; specifically, I focus on the characteristics of chemical defences secreted onto plant surfaces. Drawing from a broad literature encompassing ecology, evolution, taxonomy and physiology, I found that these external chemical defences (ECDs) are common and widespread in plants and algae; hundreds of examples have been detailed, yet they are not delineated as a separate class from internal chemical defences (ICDs). I propose a novel typology for ECDs and, using existing literature, explore the ecological consequences of the hypothesized unique characteristics of ECDs. The axis of total or proportional investment in ECDs versus ICDs should be considered as one axis of investment by a plant, in the same way as quantitative versus qualitative chemical defences or induced versus constitutive defences is considered. The ease of manipulating ECDs in many plant systems presents a powerful tool to help test plant defence theory (e.g. optimal defence). The framework outlined here integrates various disciplines of botany and ecology and suggests a need for further examinations of exudates in a variety of contexts, as well as recognition of the effects of within-plant localization of defences.