Accurate state characterization of batteries is conducive to ensuring the safety, reliability, and efficiency of their work. In recent years, ultrasonic non-destructive testing technology has been gradually applied to battery state estimation. In this paper, research on the state characterization of lithium-ion batteries based on ultrasonic guided wave (UGW) scanning is carried out. The laser Doppler vibrometer (LDV) and the X-Y stage are used to obtain the surface scanning UGW signal and the line scanning UGW signal of lithium-ion batteries under different states of charge and different aging degrees. The propagation law of UGWs in the battery is analyzed by surface scanning signals, then the energy spectrum of the signals is calculated, showing that the aging of the battery attenuates the transmission energy of UGWs. The “point” parameters are extracted from the scanning point signals. On this basis, the “line” parameters composed of line scanning multi-point signals are extracted. By analyzing the changing law of parameters during the charge–discharge process of batteries, several characteristic parameters that can be used to characterize the battery state of charge and state of health are obtained. The method has good consistency in the state characterization of the three batteries and provides a new approach for non-destructive testing and evaluation of battery states.