The lithium iron phosphate (LiFePO4) blade battery is a long, rectangular-shaped cell that can be directly integrated into battery pack systems. It enhances volumetric power density, significantly reduces costs, and is widely utilized in electric vehicles. However, the flat open circuit voltage and significant polarization differences under wide operational temperatures are challenging for accurate voltage modeling of battery management systems (BMSs). In particular, inaccurate state of charge (SOC) estimation may cause overcharging and over-discharging risks. To accurately perceive the SOC of LiFePO4 blade batteries, a SOC estimation method based on the backpropagation neural network-extended Kalman filter (BPNN-EKF) algorithm is proposed. BPNN is a neural network model that utilizes the backpropagation algorithm to update model parameters, while EKF is an optimal estimation algorithm. Firstly, dynamic working condition tests, including the New European Driving Cycle (NEDC) and high-speed working (HSW) condition tests, are conducted under a wide temperature range (−25–43 °C). HSW conditions refer to a simulated operating condition that mimics the driving of an electric vehicle on a highway. The minimum voltage of the battery system is used as the output for training the BPNN model. We derive the Kalman gain by combining the BPNN output voltage. Additionally, the EKF algorithm is employed to correct the SOC value using voltage error information. Concerning long SOC calculation intervals, capacity errors, initial SOC errors, and current and voltage sampling errors, the maximum SOC estimation RMSE is 3.98% at −20 °C NEDC, 3.62% at 10 °C NEDC, and 1.68% at 35 °C HSW. The proposed algorithm can be applied to different temperatures and operations, demonstrating high robustness. This BPNN-EKF algorithm has the potential to be embedded in electric vehicle BMS systems for practical applications.