Previous studies exploring athletes' affective experience within competition neglected the multivariate nature of the construct of affective states. The purposes of the current study were to: (a) identify affective profiles before and during competition; (b) examine if key theoretical covariates from a transactional perspective of affective states (i.e., perceived control and stress) predict membership of affective profiles; (c) explore the issue of consistency or change of affective profiles for the same individual over time (transition probabilities); and (d) examine whether precompetitive perceived control and stress impact transition probabilities. Two-hundred and 96 competitive athletes filled out self-report measures of perceived stress, perceived control, intensity and direction of positive affect (PA) and negative Affect (NA). Latent profile transition analysis revealed 5 affective profiles as a whole: low PA and NA debilitators (T1 only), high PA moderate NA facilitators, low PA high NA debilitators (T1 only), moderate PA and NA neutrals (T2 only), low PA moderate NA debilitators (T2 only). Athletes exhibited changes of affective profiles over time. High PA moderate NA facilitators reported the best psychological adjustment, as indicated by the effects of covariates (i.e., perceived control and stress) on affective profiles. Precompetitive perceived control and stress significantly predicted transition probabilities (i.e., athletes' change of affective profiles from before to during competition). As a whole, an affective profile approach may prove useful in understanding affective states as a dynamic system and have implications for intervention.