Built-up environments limit air pollution dispersion in street canyons and lead to complex trade-offs between green infrastructure (GI) usage and its potential to reduce near-road exposure. This study evaluated the effects of an evergreen hedge on the distribution of particulate matter (PM1, PM2.5, PM10), black carbon (BC) and particle number concentrations (PNCs) in a street canyon in West London. Instrumentation was deployed around the hedge at 13 fixed locations to assess the impact of the hedge on vertical and horizontal concentration distributions. Changes in concentrations behind the hedge were measured with reference to the corresponding sampling point in front of the hedge for all sets of measurements. Results showed a significant reduction in vertical concentrations between 1 and 1.7 m height, with maximum reductions of –16% (PM1 and PM10) and –17% (PM2.5) at ∼1 m height. Horizontal concentrations revealed two zones between the building façade and the hedge, with opposite trends: (i) close to hedge (within 0.2 m), where a reduction of PM1 and PM2.5 was observed, possibly due to dilution, deposition and the barrier effect; and (ii) 0.2–3 m from the hedge, showing an increase of 13–37% (PM1) and 7–21% (PM2.5), possibly due to the blockage effect of the building, restricting dispersion. BC showed a significant reduction at breathing height (1.5 m) of between –7 and –50%, followed by –15% for PNCs in the 0.02–1 µm size range. The ELPI + analyser showed a peak of ∼30 nm. The presence of the hedge led to a ∼39 ± 32% decrease in total PNCs (0.006–10 µm), suggesting a greater removal in different modes, such as a 83 ± 12% reduction in nucleation mode (0.006–0.030 µm), 74 ± 15% in ultrafine (≤0.1 µm), and 34 ± 30% in accumulation mode (0.03–0.3 µm). These findings indicate graded filtering of particles by GI in a near-road street canyon environment. This insight will guide the improved design of GI barriers and the validation of microscale dispersion models.