Yes, it will work, but the current draw on the one cable may be too high for the cable to support.
I have to ask, why would a reputable company like Corsair fit two 8-way plugs to some of their PCIe cables if they weren't confident they were capable of supplying up to 300W? Better to play safe and fit one 8-way (150W) and one 6-way (75W) plug on the lead for 225W rating instead of 300W.
As I mentioned before, if the gauge of wire used is 18AWG and the "free air" rating of 18AWG is taken as 9.5A per wire, the power rating is 9.5A x 12V = 114W per wire, or 3 x 114W = 342W (nominal) for all 3 wires. GPUs are only specified to draw up to 300W total from two 8-way connectors, so that leaves a notional reserve of 42W.
But if we take the "bunched" 3-wire de-rated maximum current per wire of 7A on 18AWG, then the maximum power that can be sustained by the PCIe lead is 3 x 7A x 12V = 252W. In that case, I would be reluctant to use both 8-way plugs on a single lead, if the GPU card requires more than 252W from the PCIe lead (not including an additional 75W max from the motherboard).
In any event, some high power GPUs using "old style" connectors are fitted with three 8-way power inputs for up to 450W (+75W from PCIe motherboard socket). For these GPUs, you'd have to use more than one double-headed PCIe power lead, i.e. at least two separate PCIe leads, or even three for peace of mind.
Perhaps double ended 8-way PCIe power leads could fail in the same manner as early 12VHPWR cables on power hungry RTX4090 cards, but I think some of those melted connectors were attributed to failing to fully mate the cable end with the GPU card. At least that's what the manufacturers claimed initially.
To answer the original question again, I personally would be happy using both 8-way plugs on a single PCIe lead, provided I had installed a "quality" PSU from a reputable manufacturer. I would
not feel confident using both plugs on a cheap and nasty PSU, purchased for less than $30. Does that help?