Droplet spreading is ubiquitous and plays a significant role in liquid-based energy systems, thermal management devices and microfluidics. While the spreading of non-volatile droplets is quantitatively understood, the spreading and flow transition in volatile droplets remains elusive due to the complexity added by interfacial phase change and non-equilibrium thermal transport. Here we show, using both mathematical modelling and experiments, that the wetting dynamics of volatile droplets can be scaled by the spatial–temporal interplay between capillary, evaporation and thermal Marangoni effects. We elucidate and quantify these complex interactions using phase diagrams based on systematic theoretical and experimental investigations. A spreading law of evaporative droplets is derived by extending Tanner's law (valid for non-volatile liquids) to a full range of liquids with saturation vapour pressure spanning from
$10^1$
to
$10^4$
Pa and on substrates with thermal conductivity from
$10^{-1}$
to
$10^3\ {\rm W}\ {\rm m}^{-1}\ {\rm K}^{-1}$
. In addition to its importance in fluid-based industries, the conclusions also enable a unifying explanation to a series of individual works including the criterion of flow reversal and the state of dynamic wetting, making it possible to control liquid transport in diverse application scenarios.