Poly(vinylidenefluoride) film (PVDF) doped with Eu(III)(NO<sub>3</sub>)<sub>3</sub>(<i>o</i>-Phenanthroline)<sub>2</sub> complex (complex <b>A</b>) was manufactured using an extrusion technique. Emission spectrum of the film was compared to spectra of the dopant and polyethylene based film. Stretching the film resulted in a sharp growth of intensity and reshaping of the luminescence spectrum. The impact of the PVDF matrix on the photoluminescence spectra of complex <b>A</b> is attributed to the Stark effect. Reasons for the increase of luminescence intensity are discussed. Quantum chemical calculations revealed a marked longwave shift of the lowest triplet and singlet energy levels of complex<b> A</b> compared to free phenanthroline. The amplification and frequency shifting of the luminescent spectrum of europium-complex-doped PVDF may lead to promising applications.