An important bio-indicator of actual plant health status, the foliar content of chlorophyll a and b (Cab), can be estimated using imaging spectroscopy. For forest canopies, however, the relationship between the spectral response and leaf chemistry is confounded by factors such as background (e.g. understory), canopy structure, and the presence of non-photosynthetic vegetation (NPV, e.g. woody elements)—particularly the appreciable amounts of standing and fallen dead wood found in older forests. We present a sensitivity analysis for the estimation of chlorophyll content in woody coniferous canopies using radiative transfer modeling, and use the modeled top-of-canopy reflectance data to analyze the contribution of woody elements, leaf area index (LAI), and crown cover (CC) to the retrieval of foliar Cab content. The radiative transfer model used comprises two linked submodels: one at leaf level (PROSPECT) and one at canopy level (FLIGHT). This generated bidirectional reflectance data according to the band settings of the Compact High Resolution Imaging Spectrometer (CHRIS) from which chlorophyll indices were calculated. Most of the chlorophyll indices outperformed single wavelengths in predicting Cab content at canopy level, with best results obtained by the Maccioni index ([R780 − R710] / [R780 − R680]). We demonstrate the performance of this index with respect to structural information on three distinct coniferous forest types (young, early mature and old-growth stands). The modeling results suggest that the spectral variation due to variation in canopy chlorophyll content is best captured for stands with medium dense canopies. However, the strength of the up-scaled Cab signal weakens with increasing crown NPV scattering elements, especially when crown cover exceeds 30%. LAI exerts the least perturbations. We conclude that the spectral influence of woody elements is an important variable that should be considered in radiative transfer approaches when retrieving foliar pigment estimates in heterogeneous stands, particularly if the stands are partly defoliated or long-lived.