No, there is always vapor over every liquid. If you leave water in an open vessel it dries out - that's because it was vaporizing all the time, even if the temperature was well below 100 deg C. If you take cold bottle from the freezer it becomes covered with mist - that's because there was water vapor present in the air, even if the temperature was well below 100 deg C.
At 100 deg C (and assuming 1 atm) pressure of vapor of water becomes identical with ambient pressure and water starts to boil. It doesn't mean there was no vapor present earlier.