Scalar dispersion from ground-level sources in arrays of buildings is investigated using wind-tunnel measurements and large-eddy simulation (LES). An array of uniform-height buildings of equal dimensions and an array with an additional single tall building (wind tunnel) or a periodically repeated tall building (LES) are considered. The buildings in the array are aligned and form long streets. The sensitivity of the dispersion pattern to small changes in wind direction is demonstrated. Vertical scalar fluxes are decomposed into the advective and turbulent parts and the influences of wind direction and of the presence of the tall building on the scalar flux components are evaluated. In the uniform-height array turbulent scalar fluxes are dominant, whereas the tall building produces an increase of the magnitude of advective scalar fluxes that yields the largest component. The presence of the tall building causes either an increase or a decrease to the total vertical scalar flux depending on the position of the source with respect to the tall building. The results of the simulations can be used to develop parametrizations for street-canyon dispersion models and enhance their capabilities in areas with tall buildings.