Herein, I(V) characteristics of the tunnel junction between the scanning tunneling microscopy (STM) Pt/Ir probe and atomically flat Au film on mica using ultrahigh vacuum STM is investigated. To ensure cleanness and flatness of the Au films, optimization of the substrate annealing and Ar plasma treatment are performed. The obtained technological parameters allow to drastically improve the reproducibility of I(V) measurements. The analysis of I(V), d²I/dV² (V), and Fowler–Nordheim plots is conducted, and the presence of the features in the bias region near 1.8 V in the form of peak and minimum, peak and anomalous extra minimum, respectively is demonstrated. The direct optical measurements confirm that the features on I(V) curves are associated with the generation of photons from the STM probe-sample gap, governed by inelastic tunneling processes. The proposed I(V) analysis approach is used for indirect sensing and investigation of the light emission in the tunnel junction offering a powerful tool for the studies of the photonic sources with deeply subwavelength dimensions.