We demonstrate a novel application of green nanosilicas (GN), prepared via an environmentally friendly route, in removing volatile organic compounds (VOCs). Herein, we aim to establish GN as viable alternatives to traditional mesoporous silicas for the removal of monoaromatic hydrocarbons (MAHC). The results show that the GN have high extraction efficiencies comparable to those previously reported for mesoporous silicas. It was demonstrated that bespoke GN can be syntheised readily with the ability to tailor their physical properties and MAHC adsorption. In order to understand the MAHC adsorption by GN, their porosity, morphology and pore structure were characterised. It was observed that the combination of broad pore size distribution and, in particular, the presence of meso- and micro-porosity in GN contributed to high MAHC extraction efficiencies and selectivity. Although from a commercial viewpoint, further optimisation of GN is desirable in order to replace traditional sorbents, this work clearly highlights a new family of “green” sorbents, which can be prepared with a substantial reduction in secondary pollution with potential applications in selective gas separation. Graphical Abstract: [Figure not available: see fulltext.]