Several effects are possible here:
1. Any mixing of a lower pH water with a higher pH water will bring down the pH of the higher one, but the change may be very small when one is buffered (tank water) and the other not so much (RO/DI water).
2. Pure water will have a pH of about 7, but it is very difficult to measure with a normal pH meter because there is little buffering and the pH swings around over several pH units. Also, trace impurities on the probe and container will dominate the pH.
3. Pure water will quickly absorb CO2 from the air, lowering the pH. Also, water getting through an RO can have quite a lot of CO2 already in it if the source water has such CO2.
4. pH probes are somewhat sensitive to other things in tank water (like sodium). Thus, if you substantially change the salinity by adding RO water, the pH can "appear" to change, when in reality the actual pH change may not be what you observe. This effect isn't likely to be important with normal salinity changes in a reef tank, but could be if you mixed large amounts of RO water with tank water in a cup.