In this paper, a network of 37 fiber Bragg grating (FBG) sensors is proposed for real-time, in situ, and operando multipoint monitoring of the surface temperature distribution on a pack of three prismatic lithium polymer batteries (LiPBs). Using the network, a spatial and temporal thermal mapping of all pack interfaces was performed. In each interface, nine strategic locations were monitored by considering a three-by-three matrix, corresponding to the LiPBs top, middle and bottom zones. The batteries were subjected to charge and discharge cycles, where the charge was carried out at 1.0 C, whereas the discharge rates were 0.7 C and 1.4 C. The results show that in general, a thermal gradient is recognized from the top to the bottom, but is less prominent in the end-of-charge steps. The results also indicate the presence of hot spots between two of the three batteries, which were located near the positive tab collector. This occurs due to the higher current density of the lithium ions in this area. The presented FBG sensing network can be used to improve the thermal management of batteries by performing a spatiotemporal thermal mapping, as well as by identifying the zones which are more conducive to the possibility of the existence of hot spots, thereby preventing severe consequences such as thermal runaway and promoting their safety. To our knowledge, this is the first time that a spatial and temporal thermal mapping is reported for this specific application using a network of FBG sensors.