I run both (LS on Mac, at least), they do different things - pi.hole is a great ad blocker which applies to all of the devices on your network. Little Snitch is doing something different - it tells you every call that every app you use is making, and allows you to approve or deny each one. So, you can block telemetry for apps, or you can block certain apps from contacting certain servers, or you can just use it to watch what apps on your system are calling out to where.
To clarify, I'm aware that pihole is not intended to run on a client OS, and doesn't monitor at a process level. I'm focused on the intended effect rather than the process itself (blocking malicious/ad servers). And I think I framed my initial question incorrectly as if LS and PiHole as subtitutes. It's perfectly fine and even preferrable to use both as layered protection. I'm just thinking however when it comes for bang-for-buck it seems like PiHole is the better value proposition if you could only set up one.
pi.hole is primarily billed as an ad blocker, but the fundamental way it works is by applying a curated set of DNS lists that are blocked (commonly telemetry and ad servers), and the admin dashboard which is just a web page (therefore works on all platforms, smartphones included) will do the same thing: it tells you every call that every app on every device on your network is making, and you can approve or deny it. You can curate your own list as well and block servers/connections you don't want on the network.
LS afaik operates in the same area where it's intended to be used for privacy. I guess I could see it being useful for people who don't have admin access to their router, but for people who do have such access I would think the benefits of network-wide DNS monitoring/blocking would outweight the costs of having to configure your router settings.