This article adds a new direction to the functional capability of protein-protected atomically precise gold clusters as sensors. Counting on the extensively researched intense luminescence of these clusters and considering the electron donating nature of select amino acids, we introduce a dual probe sensor capable of sensing changes in luminescence and conductivity, utilizing bovine serum albumin-protected atomically precise gold clusters hosted on nanofibers. To this end, we have also developed a hybrid nanofiber with a conducting core with a porous dielectric shell. We show that clusters in combination with nanofibers offer a highly selective and sensitive platform for the detection of trace quantities of trinitrotoluene, both in solution and in the vapor phase. In the solution phase, trinitrotoluene (TNT) can be detected down to 1 ppt at room temperature, whereas in vapor phase, 4.8 × 109 molecules of TNT can be sensed using a 1 mm fiber. Although the development in electrospinning techniques for fabricating nanofibers as sensors is quite substantial, a hybrid fiber with the dual properties of conductivity and luminescence has not been reported yet. © 2017 American Chemical Society.