Plants emit an extremely diverse bouquet of volatile organic compounds (VOCs) from their above-ground and below-ground parts. Emissions are constitutive or induced, e.g. by herbivores. VOCs can be classified as highly volatile, volatile and semivolatile compounds. Sesquiterpenes (SQTs) are typical semi-volatile organic compounds (sVOCs) released by plants. Similarly, herbivore-induced homoterpenes and methyl salicylate also have relatively low volatility. SVOCs have a high boiling point (> 240 °C) and a vapour pressure below 0.005 kPa at 25 °C. Glandular trichomes on plant surfaces can store SQTs in mixtures with more volatile VOCs, which are released into the air by diffusion or after gland rupture. The sVOCs stored in glandular trichomes often have repellent effects on herbivores, while herbivore-induced sVOCs are known for their attractiveness to natural enemies of herbivores, i.e. they act in indirect chemical defence of plants. Due to their low volatility, sVOCs produced by plants may easily adhere to the surfaces of emitter and neighbouring plants during the colder temperatures that plants face, e.g. at night. On the foliage of neighbouring receiver plants, sVOCs may act in direct and indirect defence of that plant species. When the temperature rises again, sVOCs are released into the atmosphere. The semi-volatile reaction products of highly volatile plant monoterpenes and photochemical pollutants such as ozone could constitute further sVOCs on plant leaf surfaces. Here, we review recent literature of the plant surface-environment interaction of biogenic sVOCs and particularly evaluate potential crop protection strategies such as intercropping and companion planting using sVOC-emitting species. Foliage typically forms the widest surfaces on crop plants, and foliar herbivory is a major type of pest damage during the vegetative stage of crop plants. Foliage is also a major source of herbivore-induced VOC emissions. Consequently, we focus on foliage-mediated sVOCs and their potential in pest management.