A megawatt-peak-power picosecond all-fiber-based laser in master oscillator power amplifier (MOPA) is experimentally demonstrated. Only 34-cm-long highly Yb3+-doped large mode area (LMA) phosphate fiber was used as the gain fiber in the amplification stage to alleviate nonlinearity and achieve high peak power. Picosecond pulses with single pulse energy of 21.2 μ J and peak power of 0.96 MW were achieved at the repetition rate of 500 kHz. Evident spectral degradation can be observed as the peak power approached 1 MW, and a stimulated Raman scattering (SRS) free peak power of 0.51 MW was obtained in the experiment. Moreover, the output power under different repetition rates was investigated.