With the exponential growth of social media, that is, blogs and social networks, organizations and individual persons are increasingly using the number of reviews of these media for decision-making about a product or service. Opinion mining detects whether the emotions of an opinion expressed by a user on Web platforms in natural language are positive or negative. This paper presents extensive experiments to study the effectiveness of the classification of Spanish opinions in five categories: highly positive, highly negative, positive, negative and neutral, using the combination of the psychological and linguistic features of LIWC (Linguistic Inquiry and Word Count). LIWC is a text analysis software that enables the extraction of different psychological and linguistic features from natural language text. For this study, two corpora have been used, one about movies and one about technological products. Furthermore, we conducted a comparative assessment of the performance of various classification techniques, J48, SMO and BayesNet, using precision, recall and F-measure metrics. The findings revealed that the positive and negative categories provide better results than the other categories. Finally, experiments on both corpora indicated that SMO produces better results than BayesNet and J48 algorithms, obtaining an F-measure of 90.4 and 87.2% in each domain.