Subambient daytime radiative cooling enables temperatures to passively reach below ambient temperature, even under direct sunlight, by emitting thermal radiation toward outer space. This technology holds promise for numerous exciting applications. However, previous demonstrations of subambient daytime radiative cooling require surfaces that directly face the sky, and these cannot be applied to vertical surfaces that are ubiquitous in real-world scenarios such as buildings and vehicles. Here, we demonstrate subambient daytime radiative cooling of vertical surfaces under peak sunlight using a hierarchically designed, angularly asymmetric, spectrally selective thermal emitter. Under peak sunlight of about 920 watts per square meter, our emitter reaches a temperature that is about 2.5°C below ambient temperature, corresponding to a temperature reduction of about 4.3° and 8.9°C compared with a silica-polymer hybrid radiative cooler and commercial white paint, respectively.