Maize (Zea Mays) is one of the most valuable food crops in sub-Saharan Africa and is a critical component of local, national and regional economies. Whereas over 50% of maize production in the region is produced by smallholder farmers, spatially explicit information on smallholder farm maize production, which is necessary for optimizing productivity, remains scarce due to a lack of appropriate technologies. Maize leaf area index (LAI) is closely related to and influences its canopy physiological processes, which closely relate to its productivity. Hence, understanding maize LAI is critical in assessing maize crop productivity. Unmanned Aerial Vehicle (UAV) imagery in concert with vegetation indices (VIs) obtained at high spatial resolution provides appropriate technologies for determining maize LAI at a farm scale. Five DJI Matrice 300 UAV images were acquired during the maize growing season, and 57 vegetation indices (VIs) were generated from the derived images. Maize LAI samples were collected across the growing season, a Random Forest (RF) regression ensemble based on UAV spectral data and the collected maize LAI samples was used to estimate maize LAI. The results showed that the optimal stage for estimating maize LAI using UAV-derived VIs in concert with the RF ensemble was during the vegetative stage (V8–V10) with an RMSE of 0.15 and an R2 of 0.91 (RRMSE = 8%). The findings also showed that UAV-derived traditional, red edge-based and new VIs could reliably predict maize LAI across the growing season with an R2 of 0.89–0.93, an RMSE of 0.15–0.65 m2/m2 and an RRMSE of 8.13–19.61%. The blue, red edge and NIR sections of the electromagnetic spectrum were critical in predicting maize LAI. Furthermore, combining traditional, red edge-based and new VIs was useful in attaining high LAI estimation accuracies. These results are a step towards achieving robust, efficient and spatially explicit monitoring frameworks for sub-Saharan African smallholder farm productivity.