A proper diet increases the effectiveness of training and accelerates post-workout regeneration. One of the factors determining eating behaviour are personality traits, including those included in the Big Five model, i.e., neuroticism, extraversion, openness, agreeableness, and conscientiousness. The aim of this study was to analyse the personality determinants of peri-exercise nutritional behaviours among an elite group of Polish athletes practicing team sports. The study was conducted in a group of 213 athletes, using the author’s validated questionnaire of exercise-related nutrition behaviours and the NEO-PI-R (Neuroticism Extraversion Openness-Personality Inventory-Revised). A statistical analysis was performed using Pearson’s linear correlation and Spearman’s rank correlation coefficients as well as a multiple regression analysis, assuming a significance level of α = 0.05. It has been shown that the level of the overall index regarding normal peri-exercise eating behaviours decreased with increasing neuroticism (r = −0.18) and agreeableness (r = −0.18). An analysis of the relationship between the personality traits (sub-scales) of the Big Five model demonstrated that the overall index of proper peri-exercise nutrition decreased with the intensification of three neuroticism traits, i.e., hostility/anger (R = −0.20), impulsiveness/immoderation (R = −0.18), and vulnerability to stress/learned helplessness (R = −0.19), and four traits of agreeableness, i.e., straightforwardness/morality (R = −0.17), compliance/cooperation (R = −0.19), modesty (R = −0.14), and tendermindedness/sympathy (R = −0.15) (p < 0.05). A multiple regression analysis exhibited that the full model consisting of all the analysed personality traits explained 99% of the variance concerning the level of the proper peri-exercise nutrition index. In conclusion, the index of proper nutrition under conditions of physical effort decreases along with the intensification of neuroticism and agreeableness among Polish athletes professionally practicing team sports.