Multi-angle remote sensing can either be regarded as an added source of uncertainty for variable retrieval, or as a source of additional information, which enhances variable retrieval compared to traditional single-angle observation. However, the magnitude of these angular and band effects for forest structure parameters is difficult to quantify. We used the Discrete Anisotropic Radiative Transfer (DART) model and the Zelig model to simulate the forest canopy Bidirectional Reflectance Distribution Factor (BRDF) in order to build a look-up table, and eight vegetation indices were used to assess the relationship between BRDF and forest biomass in order to find the sensitive angles and bands. Further, the European Space Agency (ESA) mission, Compact High Resolution Imaging Spectrometer onboard the Project for On-board Autonomy (CHRIS-PROBA) and field sample measurements, were selected to test the angular and band effects on forest biomass retrieval. The results showed that the off-nadir vegetation indices could predict the forest biomass more accurately than the nadir. Additionally, we found that the viewing angle effect is more important, but the band effect could not be ignored, and the sensitive angles for extracting forest biomass are greater viewing angles, especially around the hot and dark spot directions. This work highlighted the combination of angles and bands, and found a new index based on the traditional vegetation index, Atmospherically Resistant Vegetation Index (ARVI), which is calculated by combining sensitive angles and sensitive bands, such as blue band 490 nm/−55°, green band 530 nm/55°, and the red band 697 nm/55°, and the new index was tested to improve the accuracy of forest biomass retrieval. This is a step forward in multi-angle remote sensing applications for mining the hidden relationship between BRDF and forest structure information, in order to increase the utilization efficiency of remote sensing data.