The flow caused by natural convection adjacent to a heated vertical wall (wall flow) is an important mechanism in the creation of wind flows in a city when the background wind is weak. The wall flows along a 16-storey building were measured in Guangzhou, China. Fourteen three-dimensional ultrasonic anemometers were installed on three floors to study the boundary layer structure. Continuous measurements were taken during three test periods. The Rayleigh numbers were approximately 1013, 1013 and 1014 at the height of the 5th, 10th and 14th floors, respectively. The diurnal changes in the velocity of the wall flows, the wall surface temperature and the ambient air temperature were analysed.Our new experimental data support the theory that the natural convection boundary layer has a three-layer structure, i.e. an inner viscous layer, a transition layer and an outer turbulent layer, as first proposed theoretically by Wells and Worster. The outer turbulent layer is governed by the law of plumes with a Gaussian profile. The vertical velocity changes with g′4/9x1/3 along the vertical wall, where g′ is the buoyancy force and x is the coordinate along the vertical wall. It was noted that only the building's roof was significantly cooler than the ambient air at night, due to the sky radiation effect, so no downward flow adjacent to the wall caused by the cooling plate effect was found in our field measurements.