This paper proposes an improved initial alignment method for a strap-down inertial navigation system/global navigation satellite system (SINS/GNSS) integrated navigation system with large misalignment angles. Its methodology is based on the three-dimensional special Euclidean group and extended Kalman filter (SE2(3)/EKF) and aims to overcome the challenges of achieving fast alignment under large misalignment angles using traditional methods. To accurately characterize the state errors of attitude, velocity, and position, these elements are constructed as elements of a Lie group. The nonlinear error on the Lie group can then be well quantified. Additionally, a group vector mixed error model is developed, taking into account the zero bias errors of gyroscopes and accelerometers. Using this new error definition, a GNSS-assisted SINS dynamic initial alignment algorithm is derived, which is based on the invariance of velocity and position measurements. Simulation experiments demonstrate that the alignment method based on SE2(3)/EKF can achieve a higher accuracy in various scenarios with large misalignment angles, while the attitude error can be rapidly reduced to a lower level.