Poly (o-toluidine) (POT) doped with salicylidene-o-aminophenol (SAP) was prepared and characterized using several spectroscopic techniques. The potential (PE) and optimum molecular geometric (OMG) energies and dipole moment (μ) in kcal/mol and debbye units of the different structures of the dopant (SAP) were calculated using molecular mechanics (MM) calculations. MM calculations suggest that the optimum geometric structure (OMG) of SAP-doped POT is at least three orders of magnitude (3.69 x 103) more stable than of that of the molecular geometric structure of the same matrix. 1HNMR spectra and MM calculations described that the –OH group in the dopant (SAP) is almost free. Decrease of the absorbance at ~600 nm due to the quinoid structure of the base form of POT (POT-EB) after addition of SAP at constant concentration of POT reveals that the POT-EB was reduced to a lower oxidation state by SAP during the formation of the SAP-doped POT matrix. The detection limit for dopant (SAP) is as low as 10.66 ppm (mg/L). Transparent composite of spectroactive particles (SAP-doped POT) with the following conventional host polymers, poly (acrylic acid) (PAA), poly (methyl metha acrylate) (PMMA), poly (vinyl alcohol) (PVA), poly (ethylene glycol) (PEG), and poly (vinylpyrrolidone) (PVP) were fabricated. This transparent coating composite can be useful in certain applications such as antistatic coating in electronic industry where a visual inspection is necessary.