Evaporation of water is a fundamental and ubiquitous process that is on the ground of different types of nanoscience phenomena such as evaporation induced self-assembly. Even if water evaporation is a very basic phenomenon, there is still a lack of experiments that give a direct insight of the process. In situ application of rapid scan time-resolved infrared spectroscopy to an evaporating droplet has allowed monitoring the process at different relative humidity conditions. The experiments have been performed in the near-infrared range using water and deuterated water. The water evaporation appears as a continuous process that is not affected by changes of relative humidity in the external environment. This result, however, is affected by the impossibility to discriminate the contribution of the adsorbed water. The same experiment repeated with a deuterated water droplet has allowed, instead, a direct observation of the contribution during the evaporation process from water in the external environment. The time-resolved analysis has shown that at higher relative humidity the water adsorption is enhanced and that this process is time delayed with respect to the beginning of the evaporation process.