If you do that, ur 5V will start to charge, and even if the 5V one is rechargeable, it will probably blow up in ur face.
So basically u won't need to worry about voltage measurements.
If you run 2 batteries or v sources, like a solar panel & backup battery, provide each with a blocking diode[ OR GATE]. Running 2 12 V batteries in parallel is common in RVs, but preffer 2 6s in series.