Biodegradable control polyurethane (PU) film as well as PU nanocomposite films (PU-SWCNTs), covalently incorporated with minor amount of hydroxyl single walled carbon nanotubes [(OH)n-SWCNTs] have been formulated to investigate the influence of SWCNTs on the matrix of PU (3-dimensional network of soft and hard segments). Biodegradable polyol, polycaprolactone triol (PCL, ∼70%), diisocyanate (TDI, ∼21%) and 1, 4- butane diol (BDO) as chain extender were taken to react at 70 °C under inert atmosphere in the presence of amine catalyst (PMDETA) via prepolymer process to obtain the control PU film by casting approach, whereas in situ addition of (OH)n-SWCNTs into the above formulation can afford the covalently incorporated PU-SWCNTs films by the identical protocol. PU and PU-SWCNTs films loaded with variable quantity of (OH)n-SWCNTs (0.01, 0.03, 0.05, 0.1 and 0.3 wt.%) were characterized to identify the enhancement of their physicochemical properties such as optical, electrical conductivity, thermal and mechanical properties. These film samples were characterized by FT-IR, Raman, ATR-FT IR, UV–vis DRS, solid state 13C NMR, XRD, impedance measurements, DSC, TGA, EDX, SEM, AFM, optical microscope and tensile strength data.