We report ultrafast-laser-induced photochemical, structural, and morphological changes in a polyimide film irradiated at the polymer-glass interface in back-incident geometry. Back-illumination creates locally hot material at the interface leading to a confined photochemical change at the interface and a morphological change through a blister formation. The laser-induced photochemical changes in polyimide resulted in new absorption and luminescence properties in the visible region. The laser-treated polyimide exhibited photoluminescence anisotropy resulting from formation of ordered polymer upon irradiation by linearly polarized ultrashort laser pulses. Confocal fluorescence microscopy resulted in similar observations to the bulk. Reflection-absorption infrared spectroscopy and X-ray photoelectron spectroscopy together indicated confinement of laser-induced chemical changes at the interface.