Complexity is an important component of food and drink, especially for experience/hedonic goods such as wine. However, the contribution of the temporal aspects of the tasting experience to such top-down cognitive evaluations of wine is not well-understood. In this study, we assessed how the length of wine ageing influenced the perceived complexity and temporal evolution of flavours, as judged by wine experts (N = 22) and novices (N = 60). A total of six Madeira wines, from two grape varieties and three ageing points, were served blind. Participants first rated the complexity of each wine before using Temporal-Check-All-That-Apply (TCATA) methodology to evaluate eight taste and flavour attributes over 120 s. Finally, participants provided free-text descriptions of wine complexity. Results demonstrated that wine experts, but not novices, were able to discriminate between wines according to complexity. Moreover, TCATA results mirrored the complexity results showing experts were able to better discriminate between the samples, with older wines exhibiting different flavour trajectories and longer aftertaste durations compared to younger wines. For both novices and experts, complexity ratings were associated with the total number of attributes, flavour duration, and overall intensity, but not how much the wine changed during the tasting experience. Free-text results revealed having multiple flavours as the most important self-rated feature of wine complexity, although experts reported temporal factors more than novices. Taken together, our results indicate previously uncharted differences in how experts and novices use temporal aspects in their evaluation of wine complexity.