The relationship of open circuit voltage (OCV) versus state of charge (SOC) is critical for many techniques such as accurate battery modeling and reliable SOC estimation. However, the hysteresis existing in OCV–SOC curves of lithium-ion batteries complicates this relationship especially for lithium iron phosphate (LiFePO4) batteries which exhibit a very flat OCV–SOC hysteretic feature. This paper aims at modeling the OCV–SOC hysteresis for LiFePO4 batteries. The modeling approach is a novel adaptive discrete Preisach model (ADPM) based on the classic Preisach model and the least mean square (LMS) theory. To enhance the performance, the ADPM uses the measured current at each time step to adjust the weight vector. This method significantly decreases the errors (<1%) between the model predicted SOC and the true SOC acquired from experiments. A deformation algorithm of ADPM is further proposed to guarantee the performance even when large errors appear in the measured current. For further applications of the proposed ADPM such as SOC estimation, the robust performance of ADPM is also discussed when considering OCV input errors and measurement current errors. The results show that the maximum SOC calculation errors are about 6% and 5% respectively against uncertain OCV input and measured current which indicate the enormous potential of ADPM in battery management systems.