The issue is that the Services and Request QueryString/Form delegate caches are pre-populated on Startup before AppHost.Configure() is called (when Services are initialized) so you’d need to initialize it in your AppHost constructor, e.g:
The Services early-binding is the only reason why you’d want to define it before Configure(), so if you need it, you’d need to define it either in the AppHost constructor or outside the AppHost before appHost.Init().
ServiceStack Services are the only thing that’s initialized and registered in the IOC before AppHost.Configure() is called which is how you’re able to resolve them from the IOC and execute them on Startup.