Pollination based on insect deception has been debated in the scientific community since it was first reported over two hundred years ago. A vast majority of deceptive syndromes occur within the orchid family. While many cheating flowers have been described and are well known, there are still many curious cases that need further investigation. One prime example of such a case is Cypripedium calceolus, known as European lady’s slipper orchid. While the flower has been of interest to many prominent scientists for over a century, its pollination is still not fully understood. Both visual and olfactory cues seem to play an important role in pollinator attraction. In this study we focussed on the olfactory cues in order to explore their relationship (in future experiments) with floral visual cues, including the unique asymmetry of these flowers. Some of the plants’ floral fragrances were used in Electroantennography experiments. Eleven chemical compounds were applied to the antennae of Bombus terrestris and Apis mellifera. Even though these species are not regular visitors of C. calceolus, we were interested to see whether there were common principles in their responses to the flowers’ scent that might justify extrapolating to other pollinator species such as sand bees that get trapped in these orchids and fly out of the flowers afterwards with pollen smeared on their body. The results show that while both species react similarly to most of the odours, some of the tested acetates induced a significantly greater reaction in B. terrestris antennae. These acetates play an important role in bumblebee pheromones, but their relevance for the natural pollinators of C. calceolus remains to be confirmed to see whether chemical mimicry by these flowers is deliberately employed to attract pollinators.