Pension income splitting can occur at any age, as long as there is eligible pension income to split. The TIME MACHINE calculates the future eligible pension income, and then optimizes the amount to split using 2 criteria:
1. To equalise taxable income between the 2 spouses, so pension income can be claimed by the lower income spouse rather than the higher income spouse
2. If possible for both spouses to get the pension income tax credit, so that even a higher-income spouse can receive pension income from a lower-income spouse up to the maximum amount for the pension income credit.
There are some additional complications for Québec due to whether splitting is allowed for the health tax based on age.
RRIF withdrawals become eligible pension income only at 65 as you said. How it will be split is determined by the TIME MACHINE to try to optimise it.