Is this safe and will it work?

It should work. Some P4 Mainboards come with a molex connector aswell as their p4 connector just incase the psu has no p4 connector. Although if your psu his so old it has no p4 connector then you should probably buy a new one anyway.
 
Sorry didnt explain very well. This isnt for my current rig i was only looking into a small itx setup for torrents and fileserver and all of the tiny power supplys dont seem to have a p4 conector
 
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