In this study, the performances of a pouch Li-ion battery (LIB) with respect to temperature, pressure and discharge-rate variation are measured. A sensitivity study has been conducted with three temperatures (5 °C, 25 °C, 45 °C), four pressures (0.2 MPa, 0.5 MPa, 0.8 MPa, 1.2 MPa) and three electrical discharge rates (0.5 C, 1.5 C, 3.0 C). Electrochemical processes and overall efficiency are significantly affected by temperature and pressure, influencing capacity and charge–discharge rates. In previous studies, temperature and pressure were not controlled simultaneously due to technological limitations. A novel test bench was developed to investigate these influences by controlling the surface temperature and mechanical pressure on a pouch LIB during electrical charging and discharging. This test rig permits an accurate assessment of mechanical, thermal and electrical parameters, while decoupling thermal and mechanical influences during electrical operation. The results of the study confirm what has been found in the literature: an increase in pressure leads to a decrease in performance, while an increase in temperature leads to an increase in performance. However, the extent to which the pressure impacts performance is determined by the temperature and the applied electrical discharge rate. At 5 °C and 0.5 C, an increase in pressure from 0.2 MPa to 1.2 MPa results in a 5.84% decrease in discharged capacity. At 45 °C the discharge capacity decreases by 2.17%. Regarding the impact of the temperature, at discharge rate of 0.5 C, with an applied pressure of 0.2 MPa, an increase in temperature from 25 °C to 45 °C results in an increase of 4.27% in discharged capacity. The impact on performance varies significantly at different C-rates. Under the same pressure (0.2 MPa) and temperature variation (from 25 °C to 45 °C), increasing the electrical discharge rate to 1.5 C results in a 43.04% increase in discharged capacity. The interplay between temperature, pressure and C-rate has a significant, non-linear impact on performance. This suggests that the characterisation of an LIB would require the active control of both temperature and pressure during electrical operation.