Prefix and postfix increment/decrement operators differ in whether they increment/decrement the variable before or after assignment. With prefix (++i, --i), the operation is performed before assignment, changing the value. With postfix (i++, i--), the original value is assigned before the operation, which doesn't change the value until later. For example, if i=5, then ++i results in i=6, while i++ results in i=6 but uses the original value of 5 for any other calculations in that statement.