Land surface albedo plays an important role in controlling the surface energy budget and regulating the biophysical processes of natural dynamics and anthropogenic activities. Satellite remote sensing is the only practical approach to estimate surface albedo at regional and global scales. It nevertheless remains challenging for current satellites to capture fine-scale albedo variations due to their coarse spatial resolutions from tens to hundreds of meters. The emerging Sentinel-2 satellites, with a high spatial resolution of 10 m and an approximate 5-day revisiting cycle, provide a promising solution to address these observational limitations, yet their potentials remain underexplored. In this study, we integrated the Sentinel-2 observations with an updated direct estimation approach to improve the estimation and monitoring of fine-scale surface albedo. To enable the capability of the direct estimation approach at a 10-m scale, we combined the 10-m resolution European Space Agency (ESA) WorldCover land cover data and the 500-m resolution Moderate-Resolution Imaging Spectroradiometer (MODIS) Bidirectional Reflectance Distribution Function (BRDF)/albedo product to build a high-quality and representative BRDF training database. To evaluate our approach, we proposed an integrated evaluation framework leveraging 3-D physical model simulations, ground measurements, and satellite observations. Specifically, we first simulated a comprehensive dataset of Sentinel-2-like surface reflectance and broadband albedo across a variety of geometric configurations using the MODIS BRDF training samples. With this dataset, we built the Look-Up-Tables (LUTs) that connect surface broadband albedo and Sentinel-2 reflectance through a direct angular bin-based linear regression approach, and further coupled these LUTs with the Google Earth Engine (GEE) cloud-computing platform. We next evaluated the proposed algorithm at two spatial levels: (1) 10-m scale for absolute accuracy assessment using the references from the Discrete Anisotropic Radiative Transfer (DART) simulations and flux-site observations, and (2) 500-m scale for large-scale mapping assessment by comparing the estimated albedo with the MODIS albedo product. Lastly, we presented four examples to show the capability of Sentinel-2 albedo in detecting fine-scale characteristics of vegetation and urban covers. Results show that: (1) the proposed algorithm accurately estimates surface albedo from Sentinel-2-like reflectance across different landscape configurations (overall root-mean-square-error (RMSE) = 0.018, bias = 0.005, and coefficient of determination (R2) = 0.88); (2) the Sentinel-2-derived surface albedo agrees well with ground measurements (overall RMSE = 0.030, bias = -0.004, and R2 = 0.94) and MODIS products (overall RMSE = 0.030, bias = 0.021, and R2 = 0.97); and (3) Sentinel-2-derived albedo accurately captures seasonal leaf phenology and rapid snow events, and detects the interspecific (or interclass) variations of tree species and colored urban rooftops. These results demonstrate the capability of the proposed approach to map high-resolution surface albedo from Sentinel-2 satellites over large spatial and temporal contexts, suggesting the potential of using such fine-scale datasets to improve our understanding of albedo-related biophysical processes in the coupled human-environment system.