Enzymatic polymerization of a number of monomers in an ordered lattice on a Langmuir trough (L-T) was investigated. The assembly and polymerization of two mixed monomeric systems consisting of 4-tetradecyloxyphenol (C14PP) with phenol, and 4-hexadecylaniline (C16PA) with aniline, in various ratios were carried out. Polymerization was obtained with C14PP and phenol (in the ratio 1:10), and C16PA and aniline (in the ratio 1:2) on buffered MilliQ water (pH 7.5) using the enzyme horseradish peroxidase (HRP) at 20°C. Polymerized monolayers were then transferred to appropriate substrates for UV-Vis, third order non linear optical (NLO) properties, and thickness measurements. Thermogravimetric analysis (TGA) was performed on the final polymers. Results suggest that the lattice controlled polymerization results in highly ordered conjugated polymers with improved functional, electronic, NLO and processability properties, which form a basis for intelligent materials design and applications.