Successful shooting performance in competition is reliant on several factors such as shooting techniques and competition-associated psychological stresses. This study examined the hypothalamus-pituitary-adrenal (HPA) axis response to upcoming competition and its association with shooting outcomes in elite junior shooting players. The cortisol awakening response (CAR) and dehydroepiandrosterone (DHEA) secretion after awakening were measured for two consecutive days (the day before and on the day of competition for the selection of national shooting team members) in 19 junior men and 21 junior women players, and the shooting scores of the individual players were obtained. The total cortisol secretion during the CAR period (CARauc) increased, but total DHEA secretion during the post-awakening period (Dauc) decreased on the day of competition, compared with one day before competition. The CARauc was higher in women than in men players, whereas Dauc was higher in men than in women players across the two consecutive days. Cortisol and DHEA levels were comparable between low-scored (below the mean scores for air pistol or air rifle players) and high-scored players one day before competition. However, the CARauc on the day of competition was higher and the variations in the CARauc and molar CARauc/Dauc ratios across the two consecutive days were greater in low-scored than in high-scored men and women players. These results indicated that upcoming competition involves alterations of the CAR and DHEA secretion after the awakening period, and greater HPA response to the upcoming competition was adversely associated with shooting scores in junior shooting athletes. An important upcoming competition was perceived as a strong stressor on awakening that induced alteration in CAR and DHEA secretion after the awakening period in elite shooting players. This study observed that, irrespective of their age and period of shooting practice, the HPA axis function on the day of competition was associated with shooting outcomes in elite shooting players.