The photoinduced reorientation of dye molecules in molecular films on solid substrates has been controlled with external dc electric fields, leading to solid state structures, which are macroscopically polar, temporally stable at room temperature, and well-defined at the molecular level. A simulation based on the excitation-driven rotational diffusion of the molecules in the potential of their neighbors yielded a realistic model and indicated a collective character of the process. This shows that we are close to a quantitative comprehension of the molecular interactions within these films.