This study explores the quantitative relationship between canopy structure and the canopy escape ratio (fesc), measured as the ratio of near-infrared reflectance of vegetation (NIRv) to the fraction of absorbed photosynthetically active radiation (fAPAR). We analyzed the correlation between fesc and key indicators of canopy structure—specifically, leaf area index (LAI) and clumping index (CI)—utilizing both Sentinel-2 satellite data and in situ observations. Our analysis revealed a moderate correlation between fesc and LAI, evidenced by an R2 value of 0.37 for satellite-derived LAI, which contrasts with the lower correlation (R2 of 0.15) observed with field-measured LAI. Conversely, the relationship between fesc and CI proved to be significantly weaker (R2 < 0.1), indicating minimal interaction between foliage distribution and light escape at the canopy level. This disparity in correlation strength was further evidenced in time series analysis, which showed little phenological variation in fesc compared to LAI. Our findings elucidate the complexities of estimating fesc based on the NIRv to fAPAR ratio and underscore the need for advanced methodologies in future research to enhance the accuracy of canopy escape models.