In the present work, dinuclear complexes of salicylic acid (Sal) and 1,10-phenanthroline (Phen) were synthesized with different concentrations of Samarium ion (Sm³⁺) in Poly Vinyl Alcohol (PVA) polymer films and their structural and spectroscopic properties were investigated. Judd–Ofelt theory has been employed to estimate the several radiative parameters for SmCl₃ and Sm(Sal)₃Phen complex in PVA polymer film which are in fairly agreement between the experimental and the theoretical values supporting the J–O theory. Photoluminescence properties of the complex have been studied on 355nm and 400nm excitations in steady state as well as in time domain. On the basis of the UV–Vis absorption, FT-IR absorption, excitation, emission spectra and decay curves, spectroscopic properties of these films were studied and the photophysics involved was explained in terms of energy transfer and the RE encapsulation effect.