We report on investigating the structural and electronic properties of semiconducting and insulating layers produced in a process resembling percolation in a unique cold plasma fabrication method (plasma-enhanced chemical vapor deposition-PECVD). Amorphous carbon-tin films (Sn-C) produced from tetramethyl tin (TMT) with an acoustic-frequency glow discharge in a three-electrode reactor were investigated. The layers, after air exposure, oxidized to SnO2/Sn-C. Depending on the coupling capacitance applied to the plasma reactor, the films could be obtained in the form of an amorphous semiconductor or an amorphous insulator. We assume that the semiconductor consists of an internal network of channels auto-organized during deposition. The insulator does not demonstrate any internal structure features. An investigation on conductive filaments creating low-dimensional (LD) nanojunctions in the semiconductor and the location of energetic levels in the insulator was performed. The main parameters of the electronic band structure of the insulating film, such as the transport gap EG (5.2 eV), optical gap Eopt (3.1 eV), electron affinity Χ (2.1 eV), and ionization potential J (7.3 eV), were determined. We have demonstrated a simple approach for developing a catalyst candidate consisting of amorphous semiconductor-insulator nanojunctions for (photo)catalytic hydrogen evolution or CO2 reduction.