The HITRAN database (High-Resolution Transmission molecular absorption database) is an extremely helpful reference for selecting lines of molecular species. In the case of water vapor, a particular strong absorption line around λ ≈ 1392.5 nm is suitable for the detection of molecules, not only because of its high strength but also because it is well separated from the neighboring transitions, thus avoiding any overlap. First, we present the optical system that uses a distributed feedback (DFB) laser diode, emitting around λ ≈ 1392.5 nm with a power ≈ 3 mW and linewidth ≤ 10 MHz. For metrological needs, we are looking for a means to control the water vapor concentration in ambient air in near real time and especially when an optical chilled mirror hygrometer is used. The latter instrument is widely used due to its performance with regard to both accuracy and repeatability of measurements. Here, using the molecular absorption device the use of such an instrument is examined from the point of view of its impact on the measurement of relative humidity. This paper reports the measured frequency positions of the observed line at