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<blockquote>If I use this connector at its rated working voltage, does that automatically mean I am not complying to IEC 62368 safety standard?</blockquote>

The pattern you reference seems to assume one side of all eight signals are tied together.  If that is really true, then I don't see how to interpret <i>working voltage</i> as anything other than the RMS voltage of each signal.  In that case, it seems you are right in that this connector can't meet the standard you quote if you have signals up to the rated voltage (500 VRMS).

If I'm misinterpreting the layout diagram and each circuit is insulated from the others, then maybe the voltage spec is circuit to circuit.  In that case the spacing is higher.

<blockquote>Would the only circumstance under which this connector could be used at its rated voltage be when the design does not have to comply with safety regulations?</blockquote>

If all circuits share a common connection being, then I think you're right.

I guess their spec means their connector alone won't arc or leak with 500 VRMS signals.  That doesn't mean it's a good idea or that you might not run afoul of other rules, that it works with real boards with real humidity and dirt, etc.