Recent studies have demonstrated increased activity in brain regions associated with emotion and reward when listening to pleasurable music. Unexpected change in musical features intensity and tempo – and thereby enhanced tension and anticipation – is proposed to be one of the primary mechanisms by which music induces a strong emotional response in listeners. Whether such musical features coincide with central measures of emotional response has not, however, been extensively examined. In this study, subjective and physiological measures of experienced emotion were obtained continuously from 18 participants (12 females, 6 males; 18–38 years) who listened to four stimuli—pleasant music, unpleasant music (dissonant manipulations of their own music), neutral music, and no music, in a counter-balanced order. Each stimulus was presented twice: electroencephalograph (EEG) data were collected during the first, while participants continuously subjectively rated the stimuli during the second presentation. Frontal asymmetry (FA) indices from frontal and temporal sites were calculated, and peak periods of bias toward the left (indicating a shift toward positive affect) were identified across the sample. The music pieces were also examined to define the temporal onset of key musical features. Subjective reports of emotional experience averaged across the condition confirmed participants rated their music selection as very positive, the scrambled music as negative, and the neutral music and silence as neither positive nor negative. Significant effects in FA were observed in the frontal electrode pair FC3–FC4, and the greatest increase in left bias from baseline was observed in response to pleasurable music. These results are consistent with findings from previous research. Peak FA responses at this site were also found to co-occur with key musical events relating to change, for instance, the introduction of a new motif, or an instrument change, or a change in low level acoustic factors such as pitch, dynamics or texture. These findings provide empirical support for the proposal that change in basic musical features is a fundamental trigger of emotional responses in listeners.