In this study, we employed Multiple Internal Reflection Infrared Spectroscopy (MIR-IR) to characterize chemical bonding structures of boron doped hydrogenated amorphous silicon (a-Si:H(B)). This technique has been shown to provide over a hundred fold increase of detection sensitivity when compared with conventional FTIR. Our MIR-IR analyses reveal an interesting counter-balance relationship between boron-doping and hydrogen-dilution growth parameters in PECVD-grown a-Si:H. Specifically, an increase in the hydrogen dilution ratio (H2/SiH4) was found to cause the increase in the Si-H bonding and a decrease in the B-H and SiH2 bonding, as evidenced by the changes in corresponding IR absorption peaks. In addition, although a higher boron dopant gas concentration was seen to increase the BH and SiH2 bonding, it also resulted in the decrease of the most stable SiH bonding configuration. The new chemical bonding information of a-Si:H thin film was correlated with the various boron doping mechanisms proposed by theoretical calculations.