Yes! But also! To me it was interesting to think about how he ultimately justified that choice (as well as all his choices throughout the story).
The story of Trigun is just Vash being forced into the trolley problem time and time again, and him trying to cheat his way out of it every time. Sometimes, it works, and everyone is saved. Sometimes, it's disastrous, and many innocent people die because Vash was unwilling to kill one person.
How does he justify this to himself? It's something he clearly struggles with throughout the story. And while yes, part of it is his belief that killing someone is wrong no matter what, I think it's less about that and more about Rem. Rem died to save every person on that planet. How could he kill someone his own mother died to save? That's why there's several moments throughout the manga that Vash seems perfectly willing to kill Knives. Not only was he not saved by Rem's sacrifice, he's the one who killed her. If it was only about "killing is always wrong", Vash wouldn't be so ready to kill his brother.
Cut to the final showdown with Legato. Vash knows that if he doesn't kill Legato, Livio will die, full stop. I genuinely believe that if it was anyone else's life in danger in that moment, Vash wouldn't have done it. If it was anyone else, it's the same choice he's made hundreds of times before. So what's so special about Livio?
Wolfwood died to save Livio, exactly how Rem died to save all the humans. The only difference is that Livio is only one man. The second Livio is killed, Wolfwood's entire sacrifice was in vain, whereas there's still a whole planet of people who will keep on living even if one man has to die.
And so while yes, Vash kills someone for the first time in that moment, he's keeping to essentially the same promise. Just this time to honor Wolfwood's sacrifice instead of Rem's. That's his justification, just like how he's justified choices in the past that ultimately led to people's death, even if he didn't pull the trigger.
And it still breaks him, of course. He still hates what he's done. But in the same way he's suffered before to protect Rem's memory, he chose to suffer to protect Wolfwood's memory as well.
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