Consuming low-glycemic index (LGI) carbohydrates (CHO) before endurance exercise results in increased fat oxidation during exercise in trained men and women. It is not known if this phenomenon occurs during low intensity exercise and in untrained participants. We examined the effects of breakfasts containing high-GI (HGI) or LGI foods on substrate utilization during rest and walking exercise in sedentary women. The metabolic and appetite responses to a standard lunch consumed after exercise were also investigated. Eight healthy sedentary women completed 2 trials. On each occasion, participants were provided with a HGI or LGI breakfast 3 h before walking for 60 min. Following exercise, participants were provided with lunch and remained in the laboratory for a further 2 h. Plasma glucose and serum insulin responses (area under the curve) were higher following the HGI breakfast than following the LGI breakfast (P < 0.05). During the 3-h postprandial period, fat oxidation was suppressed following both breakfasts but remained higher in the LGI trial (P < 0.05). During exercise, total fat oxidation was also greater in the LGI trial (P < 0.001). There were no differences in the metabolic responses to lunch. Participants reported feeling fuller following lunch in the LGI trial (P < 0.05). Consuming a LGI breakfast increases fat oxidation during subsequent exercise and improves satiety during recovery in sedentary females.