Finisterre to Porto
Monbus provides bus service from Fisterra to Santiago and from Santiago to Vigo.
Renfe operates trains from Santiago to Vigo and Vigo to Valenca
Autna provides bus service from Vigo to Porto
CP provides (Celta) train service from Vigo to Porto and (Regional) service from Valenca to Porto.
Porto to Madrid
There are flights from Porto to Madrid.
There is an overnight train from Porto to Madrid.
There are CP trains connecting from Porto to Lisboa, Valenca, and Vigo. There are Renfe trains from Valenca to Vigo.
Renfe operates trains from Vigo to Madrid. Note that Renfe provides frequent service from Vigo to Barcelona.
Autna provides bus service from Porto to Vigo.
Renex and Rede Expressos provide bus service from Porto to Lisboa.
Avanza Grupo provides bus service between Lisboa and Madrid Spain.
I have not found direct bus service from Porto to Madrid ... however that does not mean it doesn't exist.
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Airports in Portugal
ANA manages airports in Portugal
http://www.ana.pt/en-US/Pages/Homepage.aspx
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Trains in Portugal
Comboios de Portugal (urban, regional, national, and international train services)
http://www.cp.pt/cp/displayPage.do?vgnextoid=87cbd5abe2a74010VgnVCM1000007b01a8c0RCRD
CP operates overnight trains from Lisboa and Porto Portugal terminating in Madrid Spain and in Hendaye France.
Renfe
http://www.renfe.com/
Autna (Vigo to Oporto)
http://www.autna.com/
Avanza
http://www.avanzabus.com/web/default.aspx
Monbus (Galacia)
http://www.monbus.es/index2.htm
Rede Expressos
http://www.rede-expressos.pt/
Renex
http://www.renex.pt/