It has been proposed that overweight individuals may be more sensitive to the food environment than others, eliciting appetite when not ‘homeostatically hungry’, termed ‘hedonic hunger’. Moreover, exposure to visual and olfactory food cues can promote increased desire for food. Therefore, the link between hedonic hunger, assessed using the Power of Food Scale (PFS) and food-cue reactivity was investigated based upon a well-established paradigm, but using a within-subjects design. We hypothesised that participants prone to hedonic hunger would report relatively enhanced appetite following the food cue, which would be comparatively resistant to initial hunger state. Sixty-two female students, aged 18–55 years, took part in a within-subject experiment, attending in counterbalanced satiated and food-deprived states, 2–3 days apart. Reactivity measures including craving and desired portion size for pizza were reported pre- and post-pizza cue exposure, together with completion of the PFS to measure ‘hedonic hunger’. In both motivational states, all appetite reactivity ratings increased post-exposure, with greater overall appetite, but not reactivity, in the food deprived condition. High PFS scorers exhibited greater appetite but not reactivity, and no interaction was found between hedonic hunger and motivational states. Thus, PFS variance was not explained by any increased reactivity in the fed condition, deemed to constitute non-homeostatic hunger elicited by the food environment. Findings did not support claims that the PFS measures non-homeostatic appetitive reactivity to the food environment. Instead, the PFS predicted greater appetite for food, irrespective of current hunger state or food cues.