The Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission to carbonaceous asteroid (101955) Bennu performed detailed mapping with a suite of instruments to characterize the composition and geology of its surface. Here we use data from the OSIRIS-REx Thermal Emission Spectrometer (OTES) instrument to investigate the relationship of OTES-derived spectral indices to other derived data products from OTES, the OSIRIS-REx Camera Suite (OCAMS), and the OSIRIS-REx Visible and InfraRed Spectrometer (OVIRS) at global and local scales. We quantitatively confirm that high values of the OTES silicate stretching slope (from ∼10 to ∼12 μm) in midday spectra that are indicative of thin and/or patchy dust cover are strongly associated with low thermal inertia (high porosity), low albedo boulders on Bennu. These high porosity boulders have brecciated textures with embedded clasts that likely originated on Bennu's parent body or during its disruption. The high porosity of these boulders is a key factor in the local production of the dust or its entrapment, as some large, brecciated boulders with a lower porosity have little evidence of dust. A second OTES spectral parameter, the silicate bending band depth near 22.7 μm applied to early evening spectra, is not correlated to thermal inertia, but is weakly to strongly correlated to albedo, OVIRS-derived 1.05 μm and 2.74 μm band depths, OVIRS-derived hydrogen abundance, and modeled nanophase troilite abundance. In several regions on Bennu there is a strong spatial relationship between these parameters, whereby areas with shallower silicate bending bands also have shallower 1.05 μm and 2.74 μm bands and lower albedo with higher nanophase troilite abundances. These correlations, combined with analysis of the silicate bending band in laboratory experiments of space weathered and mildly heated carbonaceous chondrites, suggests that decreased silicate bending band depths signify decomposition of phyllosilicates, likely Fe-bearing, due to space weathering or mild heating (<600 °C) via solar radiation during Bennu's time in near-Earth space. There is a strong association of larger silicate bending band depths in areas dominated by small rocks and unresolved material and in areas with small (≤ 25 m) craters identified as the spectrally reddest on Bennu, suggesting that this material has been more recently exposed due to impact and/or mass wasting processes. The shallowest silicate bending depths are associated with larger rocks and boulders that appear to have the longest surface exposure history, although there is band depth variation among them suggesting either initial composition variation that resulted in different responses to space weathering or heating, or varied exposure history of individual boulders themselves. We predict that any grains returned from Bennu with a significant surface exposure history will be characterized by shallower 22.7 μm, 1.05 μm and 2.7 μm band depths and increased sulfide (troilite) abundance, as well as textural and chemical evidence for phyllosilicate dehydration.