Insects can be very good learners. For example, they can form associations between a cue and a reward after only one exposure. Discrimination learning, in which multiple cues are associated with different outcomes, is critical for responding correctly complex environments. However, the extent of such discrimination learning is not well explored. Studies concerning discrimination learning within one valence are also rare. Here we ask whether Lasius niger ants can form multiple concurrent associations to different reward levels, and how rapidly such associations can be learned. We allowed individual workers to sequentially feed on up to four different food qualities, each associated with a different odour cue. Using pairwise preference tests, we found that ants can successfully learn at least two, and likely three, odour/quality associations, requiring as little as one exposure to each combination in order for learning to take place. By testing preference between two non-extreme values (i.e. between 0.4 M and 0.8 M having been trained to the qualities 0.2, 0.4, 0.8 and 1.6) we exclude the possibility that ants are only memorising the best and worst values in a set. Such rapid learning of multiple associations, within one valence and one modality, is impressive, and makes Lasius niger a very tractable model for complex training paradigms.