There are few studies of user interaction with music libraries comprising solely of unfamiliar music, despite such music being represented in national music information centre collections. We aim to develop a system that encourages exploration of such a library. This study investigates the influence of 69 users’ pre-existing musical genre and feature preferences on their ongoing continuous real-time psychological affect responses during listening and the acoustic features of the music on their liking and familiarity ratings for unfamiliar art music (the collection of the Australian Music Centre) during a sequential hybrid recommender-guided interaction. We successfully mitigated the unfavorable starting conditions (no prior item ratings or participants’ item choices) by using each participant’s pre-listening music preferences, translated into acoustic features and linked to item view count from the Australian Music Centre database, to choose their seed item. We found that first item liking/familiarity ratings were on average higher than the subsequent 15 items and comparable with the maximal values at the end of listeners’ sequential responses, showing acoustic features to be useful predictors of responses. We required users to give a continuous response indication of their perception of the affect expressed as they listened to 30-second excerpts of music, with our system successfully providing either a “similar” or “dissimilar” next item, according to—and confirming—the utility of the items’ acoustic features, but chosen from the affective responses of the preceding item. We also developed predictive statistical time series analysis models of liking and familiarity, using music preferences and preceding ratings. Our analyses suggest our users were at the starting low end of the commonly observed inverted-U relationship between exposure and both liking and perceived familiarity, which were closely related. Overall, our hybrid recommender worked well under extreme conditions, with 53 unique items from 100 chosen as “seed” items, suggesting future enhancement of our approach can productively encourage exploration of libraries of unfamiliar music.