High-energy nanosecond pulses at wavelengths beyond 2.5 μm in the mid-infrared (mid-IR) region are of significant interest for applications such as polymer processing, minimally invasive surgery, laser ranging and infrared countermeasures. While rare-earth-doped fluoride fibers provide a compact and robust platform for mid-IR pulse generation, achieving millijoule (mJ)-level nanosecond pulses beyond 3 μm remains challenging. In this work, we demonstrate high-energy nanosecond pulse generation at 3.17 μm using a master oscillator power amplifier based on a 980 nm diode-pumped Er3+/Dy3+ co-doped fluoride fiber. Seeded by an actively Q-switched oscillator operating at a 1 kHz repetition rate, the system delivers 0.68 mJ of pulse energy with a pulse width of 132 ns and a peak power of 4.8 kW, while maintaining single-transverse-mode operation (M2 = 1.2–1.3). To the best of our knowledge, this work represents the first report on mJ-level nanosecond pulse generation beyond 3 μm from a fiber-based system.