Zn₂P₂O₇: Mn was synthesized by wet chemical route and characterized by X-ray diffraction (XRD), electron paramagnetic resonance (EPR) and photoluminescence (PL) techniques. EPR spectroscopic studies confirmed the presence of both Mn²⁺ and Mn⁴⁺ ions in zinc pyrophosphate. The presence of EPR signal at g =2 is attributed to Mn²⁺ at Zn²⁺ site having octahedral coordination of oxygen whereas the presence of an EPR signal at g = 1.998 is attributed to Mn⁴⁺ at Zn²⁺ site having considerably lower symmetry due to the presence of extra interstitial oxygen ions required for charge compensation or due to the substitution of manganese at distorted 5-coordinated zinc site. Photoluminescence spectrum also shows two bands, one at 500 nm (green emission), which is attributed to the ⁴T₁ (⁴G)-⁶A₁ (⁶S)  transition of Mn²⁺ and the other centered at 686 nm (red emission), which is attributed to the electronic transition between ²E and ⁴A₂ of Mn⁴⁺.