Find following the contact details for the main mobile phone operators in Spain:

Movistar
From your Movistar phone : 609 or 1004
From any other phone : (+34) 901 123 609
Website : http://www.movistar.es

Orange
From your Orange phone : 470 or 1414
From any other phone : (+34) 902 051 200
Website : http://www.orange.es

Vodafone
From your Vodafone phone : 123
From any other phone : (+34) 607 123 000
Website : http://www.vodafone.es

Yoigo
From your Yoigo phone : 622
From any other phone : (+34) 633 800 800
Website : http://www.yoigo.com