Two-dimensional (2D) inorganic layered materials when embedded in organic polymer matrix exhibit exotic properties that are grabbing contemporary attention for various applications. Here, nanosheet morphology of molybdenum disufide (MoS2) synthesized via one-pot facile hydrothermal reaction are exfoliated in benign aqueous medium in the presence of indole to obtain a stable dispersion. These exfoliated nanosheets then act as host to template the controlled polymerization of indole. The preassembled MoS2-polyindole (MoS2-PIn) nanostructures are reorganized at the air-water interface using the Langmuir method to facilitate maximum interfacial interaction between nanosheet and polymer. This report emphasizes large area, homogeneous dispersion of uniform-sized MoS2 nanosheets (40-60 nm diameter) in the PIn matrix and the formation of stable and uniform film via the Langmuir-Schaefer (LS) method. These self-assembled, MoS2 decorated PIn LS films are characterized using atomic force microscopy (AFM) and transmission electron microscopy (TEM). The fabricated LS films in sandwiched structure Al/MoS2-PIn/ITO as the Schottky diode portrayed remarkable enhancements in charge transport properties. Our study illustrates the potential of the MoS2-PIn LS film in electronic applications and opens a new dimension for uniform dispersion of 2D materials in other polymers via the Langmuir method for device fabrication and enhancement of electrical properties.