In recent years, much effort has been put in ontology learning. However, the knowledge acquisition process is typically focused in the taxonomic aspect. The discovery of non-taxonomic relationships is often neglected, even though it is a fundamental point in structuring domain knowledge. This paper presents an automatic and unsupervised methodology that addresses the non-taxonomic learning process for constructing domain ontologies. It is able to discover domain-related verbs, extract non-taxonomically related concepts and label relationships, using the Web as corpus. The paper also discusses how the obtained relationships can be automatically evaluated against WordNet and presents encouraging results for several domains. 2007 Elsevier B.V. All rights reserved.