This study investigated the association of preoperative 25-hydroxy (25 (OH)) vitamin D levels with postoperative complications in osteoporotic hip fracture patients following surgery. We hypothesized that patients with low concentrations of 25 (OH) vitamin D might have an increased risk of developing adverse outcomes. Between January 2019 and December 2020, a retrospective observational study was conducted, including low-energy fragility fractures at the proximal femur. Regarding preoperative 25 (OH) vitamin D levels, patients were divided into two groups (<30 ng/mL and ≥30 ng/mL). Early and late postoperative complications were assessed and graded according to the Clavien–Dindo classification system. Logistic regression analysis was performed to demonstrate the association between preoperative 25 (OH) vitamin D levels (<30 ng/mL, ≥30 ng/mL) and postoperative complications after adjusting for age and sex. Of 314 patients, 222 patients (70.7%) had a 25 (OH) vitamin D level of <30 ng/mL. The mean serum 25 (OH) vitamin D level was 22.6 ng/mL (SD 13.2). In 116 patients (36.9%), postoperative complications were observed, with the most occurring in the short term (95 patients, 30.2%). Late postoperative complications were present in 21 patients (6.7%), most graded as Clavien I (57.1%). Logistic regression analysis identified a low vitamin D level (<30 ng/mL) as an independent risk factor for early postoperative complications (OR 2.06, 95% CI 1.14–3.73, p = 0.016), while no significant correlation was found in late complications (OR 1.08, 95% CI 0.40–2.95, p = 0.879). In conclusion, preoperative 25 (OH) vitamin D serum level might be an independent predictor for early postoperative complications. However, future studies are warranted to determine risk factors for long-term complications and establish appropriate intervention strategies.