Semantically ambiguous and emotional words occur frequently in language, and the different meanings of ambiguous words can sometimes have different emotional loads. For example, the Spanish word heroína (heroin/heroine) can refer to a drug or to a woman who performs a heroic act. Because both ambiguity and emotionality affect word processing, there is a need for normative databases that include data on the emotionality of the different meanings of such words. Thus far, no bases of this type are available in Spanish. With this in mind, the current study will present meaning-dependent affective (valence) ratings for 252 Spanish ambiguous words. The analyses performed show that (a) among ambiguous words, those words with meanings that have distinct affective valence are quite frequent, (b) ambiguous words rated as neutral in isolation can have meanings of opposite valence (i.e., negative-positive or positive-negative), and (c) the valence estimated for ambiguous words in isolation is better explained by the weighted average of the valence of their meanings by dominance. A database of this kind can be useful both for basic research (e.g., relationship between emotion and language and ambiguity processing) and for applied research (e.g., cognitive and emotional biases in emotional disorders and second language learning).