The DI will grab anything the RO misses. Depending on your tap water, what comes out of the membrane can still have a decent amount of TDS, as a RO membrane only pulls out a certain percent(its efficiency).
For example....if your tap TDS is 300 and your RO membrane has a 97% rejection.....you will still be left with 9 TDS. Far from the end of the world, but DI is cheap enough to run fro such a small amount of TDS.
Some will just refer to RODI water as RO water though......