Vocal bursts are non-linguistic affectively-laden sounds with a crucial function in human communication, yet their affective structure is still debated. Studies showed that ratings of valence and arousal follow a V-shaped relationship in several kinds of stimuli: high arousal ratings are more likely to go on a par with very negative or very positive valence. Across two studies, we asked participants to listen to 1,008 vocal bursts and judge both how they felt when listening to the sound (i.e. core affect (...) condition), and how the speaker felt when producing it (i.e. perception of affective quality condition). We show that a V-shaped fit outperforms a linear model in explaining the valence-arousal relationship across conditions and studies, even after equating the number of exemplars across emotion categories. Also, although subjective experience can be significantly predicted using affective quality ratings, core affect scores are significantly lower in arousal, less extreme in valence, more variable between individuals, and less reproducible between studies. Nonetheless, stimuli rated with opposite valence between conditions range from 11% (study 1) to 17% (study 2). Lastly, we demonstrate that ambiguity in valence (i.e. high between-participants variability) explains violations of the V-shape and relates to higher arousal. (shrink)