WinUI3 can be used in unpackaged apps (I.e.: not appx) but has a few random caveats that just don’t work; random APIs that have a footnote of “oh this doesn’t work in unpackaged apps” or “works in unpackaged apps but only in .NET Preview something-something”.
.NET 8 fixes a lot of this by adding AOT compilation and single-binary releases, but it’s still fairly large. .NET 9 then improves culling of unused framework code from your published file, and also adds WPF -> WinUI3 theming support.
Source: my repeated attempts to rewrite our product’s UI in WinUI3 (from WPF on .NET Framework 3.5) several times.