Both synthetic polyesteramides have proved to be biocompatible and to act as non-viral vectors in Gene Therapy, transfecting DNA to the nucleus cell. By dip coating technique both polymers self-organize in round nanoclusters about 5 nm thick, observed by AFM, after 3h and 21h grown on Si(100) substrate, deposited in conglomerates about 300 nm, 35 nm high. When dispersed in solution, their helical molecules self-organize on metal and semiconductor surfaces. Morphology of powdered PNOBDME exhibits homogeneous spherical clusters of about 5 m in diameter homogeneously dispersed. Optical rotatory dispersion (ORD) is evaluated. Thermal behavior of the new compounds is studied by TG and DSC analysis. The two 1 H independent sets of signals observed for each enantiomer is attributed to two diastereomeric conformers: gg and gt, of the torsion containing the asymmetric carbon atom in the spacer. Molecular models show helical polymeric chains with stereo regular head-tail, isotactic structure, explained as due to the higher reactivity of the primary hydroxyl with respect to the secondary one in the glycol through the polycondensation reaction. Two new multifunctional polyesteramides designed as PNOBDME (C34H38N2O6)n: poly and PNOBEE (C26H22N2O6)n: poly, are synthesized as cholesteric liquid crystal, characterized by 1 H and 13 C-NMR, COSY and HSQC and compared to precursor polyesters.