My best guess is that %Config is some kind of tied or magic-applied hash and it doesn't like having its elements aliased

Yes, in order for MinGW to work with ActivePerl, it's necessary to override a number of %Config values. They do this with something along the lines of:
my $obj = tied %Config::Config; if(mingw_detected) { $obj->{cc} = 'gcc'; $obj->{make} = 'dmake'; .... }
I still don't get how the presence (and loading) of an empty blib can make a difference to the loading of Devel::CheckLib ... though it's probably not as important as I first thought.

I'll see how I go with what you've come up with already. Thanks !

Cheers,
Rob

In reply to Re^2: Devel::CheckLib problem by syphilis
in thread Devel::CheckLib problem by syphilis

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