Background: Surgery is usually the best treatment for patients with femoral fractures. However, the incidence of perioperative adverse outcomes in such cases is quite high. Nutrition has a major influence on fracture healing, and malnutrition is associated with higher complication rates, higher mortality rates, and longer hospitalisation periods. In this study, we aimed to identify independent risk factors and assess the predictive value of the prognostic nutritional index (PNI) for perioperative adverse outcomes in patients with femoral fractures. Methods: This retrospective observational study included 343 patients who underwent surgery for a single femur fracture at the Affiliated Hospital of Zunyi Medical University in 2018. Binary logistic regression analysis was applied to identify significant independent risk factors. The discriminatory ability of independent predictors was assessed using the receiver operating characteristic curve analysis, and DeLong's test was used to compare the area under the curve (AUC). Results: In total, 159 patients (46.4%) had perioperative adverse outcomes. PNI (OR: 0.819, 95% CI: 0.754–0.889, P < 0.001), age (OR: 1.042, 95% CI: 1.020–1.066, P < 0.001), time to admission (OR: 1.404, 95% CI: 1.117–1.765, P = 0.004), hypertension (OR: 1.912, 95% CI: 1.049–3.488, P = 0.034), combined injures (OR: 2.739, 95% CI: 1.338–5.607, P = 0.006), and operation types (OR: 3.696, 95% CI: 1.913–7.138, P < 0.001) were independent factors for perioperative adverse outcomes. Based on the AUC (PNI: 0.772, 95% CI: 0.723–0.821, P < 0.001; age: 0.678, 95% CI: 0.622–0.734, P < 0.001; time to admission: 0.585, 95% CI: 0.525–0.646, P = 0.006), the PNI had the optimal discrimination ability, indicating its superiority over other independent predictors (age vs. PNI, P = 0.002; time to admission vs. PNI, P < 0.001). Conclusions: This study showed that the PNI was a better and effective independent predictor of perioperative adverse outcomes in patients with femoral fractures. Our findings suggest that nutritional assessment at admission and appropriate intervention strategies are necessary for patients with femoral fractures.