We present ail original approach to structure the quadratic non-linear optical properties of doped polymers based on photopolymerizable resins. The orientation of the push-pull molecules incorporated in the material is locked by the polymerization process induced by an exposure to a visible light. The freeze of the orientation was investigated through second harmonic generation and infrared spectroscopy measurements. A mean relaxation time of over 4200 h was obtained with co-polymerizable chromophores. With the purely optical method we developed, one can durably photo-pattern the quadratic optical properties of photopolymers for applications in integrated optics. (C) 2003 Elsevier B.V. All rights reserved.