Steam (actually, water vapor) above a rapidly boiling can be hotter than the average temperature of the liquid because the situation is not in equilibrium.
Macroscopically, consider that in nucleate boiling the greater part of water in the container is not boiling; only in certain parts of the vessel has the water been superheated, and then flashes into vapor. "When the temperature difference is [sufficient], isolated bubbles form at nucleation sites and separate from the surface... [at a greater temperature difference] the vapor escapes as jets or columns which subsequently merge into slugs of vapor."
Those regions that formed bubbles were above the boiling point of water. Though the temperature of the bubble drops due to rapid expansion, it must still be above 100 °C or it would condense before reaching the surface (That oscillation of bubbles forming and collapsing can be observed at an incipient boil , i.e., liquid entrainment stage of boiling.). Therefore, the vapor immediately released from the bubble can be hotter than the body of the liquid, which can be verified by putting a thermometer in the spout of a steaming kettle and in the liquid.
On a microscopic level, consider the fastest moving particles, i.e, the hottest, are the ones that escape. Of course, that is on average, since there can be areas in the liquid that are superheated and have not yet boiled.
Note, though, that in film boiling, the Leidenfrost effect maintains a layer of exceedingly hot water vapor against the surface of the container, below the level of the water! Of course, that is not liquid water, but it is below the surface of the water... so the answer to your question depends on the rate of boiling and where in the container you measure the temperature.