Environmental factors controlling silicon (Si) accumulation in terrestrial plant are key drivers to alleviate plant biotic stresses, including insect herbivory. While there is a general agreement on the ability of Si-enriched plant to better resist insect feeding, recent studies suggest that Si also primes biochemical defense pathways in various plant families. In this review, we first summarize how soil parameters and climate variables influence Si assimilation in plants. Then, we describe recent evidences on the ability of Si to modulate plant volatile emissions, with potential cascade effects on phytophagous insects and higher trophic levels. Even though the mechanisms still need to be elucidated, Si accumulation in plants leads to contrasting effects on the levels of the three major phytohormones, namely jasmonic acid, salicylic acid and ethylene, resulting in modified emissions of plant volatile organic compounds. Herbivore-induced plant volatiles would be particularly impacted by Si concentration in plant tissues, resulting in a cascade effect on the attraction of natural enemies of pests, known to locate their prey or hosts based on plant volatile cues. Since seven of the top 10 most important crops in the world are Si-accumulating Poaceae species, it is important to discuss the potential of Si mobility in soil-plant systems as a novel component of an integrated pest management.