Pneumatic separation was used to separate the valuable current collectors and harmful separators in spent lithium-ion batteries (LIBs) to avoid the plastic pollution caused by the separators in this study. Theoretical calculations for suspension velocities of the current collectors and separators indicate that they could be separated under special conditions. Furthermore, a special Z-shaped pneumatic separator was used to separate the current collectors and separators for the first time. Experiments for manually cut samples indicate that the efficiency of pneumatic separation is approximately 100% with the sizes and airflow velocities in the range of 3–4 cm and 6.96–7.8 m/s, respectively. Furthermore, industrial experiments of pneumatic separation indicate that the recoveries of the current collectors and separators are approximately 99.23% and 98.64%, respectively. Computer simulations of the separation process indicate that the turbulence and the changes in high-speed zones in the pneumatic separator benefit the separation of current collectors and separators. In conclusion, pneumatic separation is a promising technology to separate crushed current collectors and separators.