Olive (Olea europaea L.) is an important woody oil crop worldwide, and accurate estimation of leaf chlorophyll content is critical for assessing nutritional status, photosynthetic capacity, and precision crop management. Unmanned aerial vehicle (UAV) remote sensing, with high spatiotemporal resolution, has increasingly been applied in crop growth monitoring. However, the small, thick, waxy leaves of olive, together with its complex canopy structure and dense arrangement, may reduce estimation accuracy. To identify sensitive features related to olive leaf chlorophyll and to evaluate the feasibility of UAV-based estimation methods for olive trees with complex canopy structures, UAV multispectral orthophotos were acquired, and leaf chlorophyll was measured using a SPAD (Soil Plant Analysis Development) meter to provide ground-truth data. A dataset including single-band reflectance, vegetation indices, and texture features was built, and sensitive variables were identified by Pearson correlation. Modeling was performed with linear regression (LR), Random Forest (RF), Extreme Gradient Boosting (XGBoost), Partial Least Squares Regression (PLSR), and Support Vector Machine (SVM). Results showed that two spectral bands (green and red), one vegetation index (TCARI/OSAVI), and twelve texture features correlated strongly with SPAD values. Among the machine learning models, XGBoost achieved the highest accuracy, demonstrating the effectiveness of integrating multi-feature UAV data for complex olive canopies. This study demonstrates that combining reflectance, vegetation indices, and texture features within the XGBoost model enables reliable chlorophyll estimation for olive canopies, highlighting the potential of UAV-based multispectral approaches for precision monitoring and providing a foundation for applications in other woody crops with complex canopy structures.