Trees play a vital role in urban cooling. The present study tested if key canopy characteristics related to tree shade could be used to predict the cooling potential across a range of urban surface materials. During the austral summer of 2018–2019, tree and canopy characteristics of 471 free-standing trees from 13 species were recorded across Greater Sydney, Australia. Stem girth and tree height, as well as leaf area index and ground-projected crown area was measured for every tree. Surface temperatures were recorded between noon (daylight saving time) and 3:00 p.m. under the canopy of each tree in the shade and in full sun to calculate the temperature differential between adjacent sunlit and shaded surfaces (∆Ts). The limited control over environmental parameters was addressed by using a large number of randomly selected trees and measurement points of surface temperatures. Analyses revealed that no systematic relationship existed among canopy characteristics and ∆Ts for any surface material. However, highly significant differences (p < 0.001) in ∆Ts existed among surface materials. The largest cooling potential of tree shade was found by shading bark mulch (∆Ts = −24.8 °C ± 7.1), followed by bare soil (∆Ts = −22.1 °C ± 5.5), bitumen (∆Ts = −20.9 °C ± 5.8), grass (∆Ts = −18.5 °C ± 4.8) and concrete pavers (∆Ts = −17.5 °C ± 6.0). The results indicate that surface material, but not the tree species, matters for shade cooling of common urban surfaces. Shading bark mulch, bare soil or bitumen will provide the largest reductions in surface temperature, which in turn results in effective mitigation of radiant heat. This refined understanding of the capacity of trees to reduce thermal loads in urban space can increase the effectiveness of urban cooling strategies.