I haven't thought hard about this, but my guess is suicide hotline volunteers aren't that stellar and you could counterfactually save 1-5 more lives per day by volunteering and being great at your job. I'm making some low-confidence guesses about the number of calls you would get per day.
If you exclude heavy-tailed bets I think the current cost to save a life is something like $3000 - $6000, so you're saving more lives than if you earn to give and donate to malaria charities.
Is there a reason this isn't recommended more?
I answered calls for Samaritans for about a year, and answered texts on Shout for about the same amount of time before that. From my own experience, I'd say 1 to 5 lives per day is extremely optimistic, for the following reasons:
I'm not aware of any trials of this kind of intervention, but they could be done. E.g. introducing a new hotline service in a country that doesn't currently have one, but only for a randomly selected half of districts/counties/states, and then comparing the impact on suicide rates over time.
My own unscientific feeling from doing this was that I probably helped a lot of people feel better that day / deal with some kind of crisis, but probably directly prevented very few suicides, if any.
Edit: thinking about the numbers a bit: there are ~6500 suicide deaths in the UK per year. Samaritans has something like 150 people answering phones 24/7 (extremely rough). So if every one of those 6500 people calls (absurd) and if the service improved so much they all survived (also absurd) that's still only 0.04 lives per person day (taking a day as 8 hours). So I think you have to start there and maybe go down a few OOMs due to those absurdly optimistic assumptions.