The Langmuir monolayers of a chloroform soluble dimethoxy substituted precursor poly(p-phenylenevinylene) (PPV) with a methoxy leaving group were studied. During storage in chloroform the precursor polymer is partly converted to PPV. Multilayer films could only be prepared of this partly converted precursor. When a monolayer of this polymer containing 5% PPV units was deposited an orientation of the polymer chain along the dipping direction was found. Whereas a monolayer containing 14% PPV units showed no orientation in the dipping direction. It is assumed that a monolayer of the precursor containing 5% PPV units can be considered as a 2D flexible network and the obtained orientation in the dipping direction is due to stretching of this network during deposition.