Flexible composite phase change materials (CPCMs) have been extensively studied in the thermal management of cylindrical lithium-ion batteries and proven to have a good cooling effect. However, passive cooling of pouch lithium-ion batteries with severe uneven temperature distribution has not received the attention it deserves. The thermal management of pouch battery based on passive cooling of flexible PCMs considering the heat-generating structure of pouch batteries needs to be further studied. Herein, CPCMs with different thermal conductivity were prepared, and four different distribution modes of CPCMs, including partial coverage and complete coverage, were applied to thermal management of pouch battery. Results indicated that the maximum temperature (Tmax) and maximum temperature difference (ΔTmax) can be kept separately within 35 °C and 5 °C in the passive thermal management of a single battery except upper coverage at discharge rate of 5C, and the middle coverage (case B) showed excellent temperature control in partial coverage cases. Equally noteworthy was that the increase in thermal conductivity increased the ΔTmax in partial coverage cases, while showing the opposite trend for full coverage (case ABC). Furthermore, only passive cooling of pouch battery pack did not meet the safety requirements under the discharge rate cycle of 5C. Under the active–passive combination mode, case B can control the Tmax (32.22 °C) and ΔTmax (4.69 °C) within a safe range, which was superior to case ABC (Tmax = 35.53 °C, ΔTmax = 5.04 °C). This conclusion provides technical support for the pouch battery to seek economic, stable and efficient thermal management.