Two-photon ionization of aromatic molecules in polymer solids and the backward charge recombination (CR) are reviewed. Spatial distribution of the ejected electrons was directly evaluated by using multilayered nanostructures of ultrathin polymer films. This evaluation does not need to assume kinetic parameters, which are unknown but essential for the conventional evaluation based on the Laplace inverse transformation of the isothermal luminescence (ITL). We demonstrated that the ejected electrons are distributed a few nanometers away from the donor layers. The backward CR is enhanced by applied electric field and heating. The electric-field stimulated ITL is explained by asymmetric CR due to distortion of the Coulomb potential of the parent cation. Thermoluminescence (TL) is stimulated by sub-transitions of polymer solids. Trap depth for ejected electrons is deepened in poly (alkyl methacrylate) solids with increasing temperature because of chemical reactions while it remains constant in polystyrene (Pst).