Little Snitch is intended for per-process, per-connection blocking - for example, you may need, eg, an Instagram uploader app to contact Meta's servers, but an unrelated app should not be able to (and even in the case of the hypothetical IG uploader, you can get very fine grained about the controls - media.facebook.net, not telemetry.facebook.net). In that way, LS does have some advantages over pi.hole in that space - You'd need to set up every single item that you normally get for free from a blocklist, but it gives you much finer control over what's getting blocked and much better visibility into what connections your processes are trying to make.
Again, I don't think Little Snitch is the right answer if you're looking for ad blocking specifically, and if that's the extent of your privacy concerns, pi.hole's a better bet. Little Snitch is a per-application connection monitor and firewall - it _can_ block ads, but that's not its primary purpose.
I would guess that to the extent the blocklists include things that are loaded by applications and not websites, they are almost entirely built by users of something like LittleSnitch or OpenSnitch. This is also entirely doable with wireshark logs, but I think that requires more infrastructure to build into usable lists.
Some telemetry might not be recognized by pi-hole as it is new or has nothing to do with ads.