The effects of background music on learning and memory are inconsistent, partially due to the intrinsic complexity and diversity of music, as well as variability in music perception and preference. By stripping down musical harmony to its building blocks, namely discrete chords, we explored their effects on memory formation of unfamiliar word-image associations. Chords, defined as two or more simultaneously played notes, differ in the number of tones and inter-tone intervals, yielding varying degrees of harmonic complexity, which translate into a continuum of consonance to dissonance percepts. In the current study, participants heard four different types of musical chords (major, minor, medium complex, and high complex chords) while they learned new word-image pairs of a foreign language. One day later, their memory for the word-image pairs was tested, along with a chord rating session, in which they were required to assess the musical chords in terms of perceived valence, tension, and the extent to which the chords grabbed their attention. We found that musical chords containing dissonant elements were associated with higher memory performance for the word-image pairs compared with consonant chords. Moreover, tension positively mediated the relationship between roughness (a key feature of complexity) and memory, while valence negatively mediated this relationship. The reported findings are discussed in light of the effects that basic musical features have on tension and attention, in turn affecting cognitive processes of associative learning.