Postoperative pneumonia (POP) is a common complication after hip fracture surgery and is associated with increased mortality and other complications in elderly patients. This study aims to evaluate biomarkers, especially the glucose-albumin ratio (GAR), for predicting POP in elderly hip fracture patients. A total of 1279 elderly patients admitted to our hospital with hip fractures were included. We assessed 29 biomarkers and focused on GAR to determine its prognostic and predictive value for POP. Multivariable logistic regression and propensity score-matched analyses were conducted to calculate adjusted odds ratios (ORs) and 95% confidence intervals (CIs) for POP, adjusting for potential confounders. Receiver operating characteristic (ROC) curves were utilized to determine the optimal cut-off of GAR for predicting POP. Among the biomarkers and combinations assessed, GAR demonstrated superior predictive capability for POP in elderly hip fracture patients. ROC analyses showed moderate predictive accuracy of GAR for POP, with an area under the curve of 0.750. Using the optimal cut-off of 0.175, the high GAR group was significantly associated with increased odds of POP (adjusted OR 2.14, 95%, CI 1.50–3.05). These associations remained significant after propensity score matching and subgroup analyses. Dose–response relationships between GAR and POP were observed. In conclusion, GAR may be a promising biomarker to predict POP risk in elderly hip fracture patients. Further studies are warranted to validate its clinical utility. However, this study has certain limitations, including its retrospective design, potential for selection bias due to the exclusion criteria, and the single-center nature of the study, which should be addressed in future prospective, multicenter studies.