Quick motherboard power questions about 4-pin + molex!

All right, so my PC, which has an ASUS Rampage V Extreme board, is connected to my PSU via 24-pin and the 8pin CPU power cable.
Now, I noticed there's two more power connectors.
One 4-pin, and one molex (technically also 4-pin but... yeah)
From what I understand, the molex one should only be used when there's more than one GPU in the system. True or false?
And, in what scenario do I need to plug in the other 4-pin cable? Overclocking?

Reply to baterax
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