Calixarenes are a novel type of molecules for nonlinear optics. In a single molecule four pi-conjugated systems are combined. Corona poled guest-host polymer systems [calixarenes-poly(methyl-methacrylate)] with transparency into the UV and loading up to 100% show a high degree of orientation. The maximum resonant d33 nonlinear coefficient measured at a fundamental wavelength of 590 nm is 51 pm/V. The d33 values of the thin films relax after poling to 65% of their maximum value. Results indicate self-organization of the molecules upon poling.