Nanocrystalline Zn₂P₂O₇:Sm³⁺ was synthesized using citrate precursor route. Rietveld refined XRD shown the formation of pure phase at 900 °C. Based on scanning electron microscopy, size distribution of the pyrophosphate particle was found to be in the range of 50–100 nm. Upon near UV light excitation (403 nm), Zn₂P₂O₇:Sm³⁺exhibits host emission at 450 nm along with characteristic emission lines of Sm³⁺. Based on PL decay measurement, it was inferred that two different types of Sm³⁺ions were present in the zinc pyrophosphate. The first type was a short lived species (~τ = 100 μs) present at less symmetric ‘5-coordinated Zn’ sites, while the second was a long lived species (~τ = 1.9 ms) present at symmetric ‘6-coordinated Zn’ sites. The color coordinates of the system were evaluated using CIE index diagram to be 0.36 and 0.37, which suggest that the prepared material is a potential near white light emitting phosphor.