Instructions
Set the Canon 5D into "Program" mode, using the dial on the top of the camera body.
Press the menu button. The rear curtain sync is a custom function and can be accessed on the camera body through the menu screens. Scroll down and select the option for "Custom Functions," then press "OK".
Scroll to custom function No. 15 and press the "Select" button. Change this setting from "0" to "1" to enable the rear curtain flash.
Connect a flash unit to the hot shoe mount on the 5D camera body. When fired, the unit's flash will synchronize with the shutter's closing.