Laser pulse amplification by a high-pressure CO2 amplifier in the long-wave infrared (LWIR) spectral range is a feasible technology for strong-field physics research. Crystals such as ZnGeP2 (ZGP) have high nonlinear coefficients and transmittance in the LWIR region, with spectral widths of generated pulses closely matching the gain spectrum of high-pressure CO2 amplifiers. Therefore, ZGP optical parametric oscillation (OPO) may allow higher-efficiency energy extraction in amplifiers, improving the output characteristics of LWIR amplification systems. In this study, the gain measurement of ZGP OPO pulses amplified by a high-pressure CO2 amplifier was carried out for the first time. Single-detector acquisition was utilized to achieve a unified sensor responsivity, and a laser signal-triggered function generator was used to synchronize the seed pulse and amplifier. Six-pass amplification was performed successively, yielding an amplification factor of 4.5 for the peak power and a maximum coefficient of 0.42% cm−1 for the small-signal gain. The gain and loss effect during small-signal amplification were discussed. The potential capability of acquiring ultra-short pulses with ZGP OPO pulses was also explored with the FFT function of MATLAB software.