Thanks for the reply.

I supplied the linker with the proper library files, what else is there to do?
The x64 reference in the error output is due to me changing the platform between win32 and x64 in VS while troubleshooting. Both options makes the same error

Code:
<Release>
C/C++ -> General: G:\libpqxx-4.0\include\pqxx
                  G:\libpqxx-4.0\config\sample-headers\compiler\VisualStudio2010\pqxx

LINKER -> General: G:\libpqxx-4.0\lib
                   C:|\PostgreSQL\9.1\lib

LINKER -> General -> input -> Additional Dependacies: libpqxx.lib
                                                      libpqxx_static.lib
                                                      libpq.lib
----------------------------------------------------------------------------------------
<Debug>
C/C++ -> General: G:\libpqxx-4.0\include\pqxx
                  G:\libpqxx-4.0\config\sample-headers\compiler\VisualStudio2010\pqxx

LINKER -> General: G:\libpqxx-4.0\lib
                   C:|\PostgreSQL\9.1\lib

LINKER -> General -> input -> Additional Dependacies: libpqxxD.lib