Not exactly. If you create an app that's specifically a "Universal" app, then no, you will not have access to win32 APIs, with or without WinUI 3.0.
However, you can create WPF or WinForms apps that make use of "Xaml Islands". Xaml Islands allow you to host UWP controls. Therefore, you will be able to host WinUI 3.0 controls in your WPF/WinForms app while also making use of win32 APIs.
There is also a rumored "Xaml Desktop" format that will come out alongside WinUI 3.0. This is expected to allow you to create Visual Studio projects with WinUI as the main UI framework while supporting win32 without having to use Xaml Islands. There's not much detail on how this will work yet, but we know that this will not be considered a true universal app (meaning you can only create these apps for desktop).