Metal chalcogenophosphates are receiving increasing interest, specifically as promising infrared nonlinear optical (NLO) candidates. Here, a rare‐earth chalcogenophosphate Eu2P2S6 crystallizing in the monoclinic noncentrosymmetric space group Pn was synthesized using a high‐temperature solid‐state method. Its structure features isolated P2S64− dimer, and two types of EuS8 bicapped triangular prisms. Eu2P2S6 exhibits a phase‐matchable second‐harmonic generation (SHG) response ≈0.9×AgGaS2@2.1 μm, and high laser‐induced damage threshold of 3.4×AgGaS2, representing the first rare‐earth NLO chalcogenophosphate. The theoretical calculation result suggests that the SHG response is ascribed to the synergetic contribution of P2S64− dimers and EuS8 bicapped triangular prisms. This work provides not only a promising high‐performance infrared NLO material, but also opens the avenue for exploring rare‐earth chalcogenophosphates as potential IR NLO materials. Eu2P2S6 exhibits excellent NLO properties, including a phase‐matchable second‐harmonic generation (SHG) response ≈0.9×AgGaS2@2.1 μm, and a high laser‐induced damage threshold of 3.4×AgGaS2. Eu2P2S6 is the first NLO‐active rare‐earth‐based chalcogenophosphate.