Reunion Island (21° S, 55° E), situated in the Indian Ocean at about 800 km east of Madagascar, is appropriately located to monitor the outflow of biomass burning pollution from Southern Africa and Madagascar, in the case of short-lived compounds, and from other Southern Hemispheric landmasses such as South America, in the case of longer-lived species. Ground-based Fourier transform infrared (FTIR) solar absorption observations are sensitive to a large number of biomass burning products. We present in this work the FTIR retrieval strategies, suitable for very humid sites such as Reunion Island, for hydrogen cyanide (HCN), ethane (C2H6), acetylene (C2H2), methanol (CH3OH), and formic acid (HCOOH). We provide their total columns time-series obtained from the measurements during August–October 2004, May–October 2007, and May 2009–December 2010. We show that biomass burning explains a large part of the observed seasonal and interannual variability of the chemical species. The correlations between the daily mean total columns of each of the species and those of CO, also measured with our FTIR spectrometer at Reunion Island, are very good from August to November (R ≥ 0.86). This allows us to derive, for that period, the following enhancement ratios with respect to CO: 0.0047, 0.0078, 0.0020, 0.012, and 0.0046 for HCN, C2H6, C2H2, CH3OH, and HCOOH, respectively. The HCN ground-based data are compared to the chemical transport model GEOS-Chem, while the data for the other species are compared to the IMAGESv2 model. We show that using the HCN/CO ratio derived from our measurements (0.0047) in GEOS-Chem reduces the underestimation of the modeled HCN columns compared with the FTIR measurements. The comparisons between IMAGESv2 and the long-lived species C2H6 and C2H2 indicate that the biomass burning emissions used in the model (from the GFED3 inventory) are probably underestimated in the late September–October period for all years of measurements, and especially in 2004. The comparisons with the short-lived species, CH3OH and HCOOH, with lifetimes of around 5 days, suggest that the emission underestimation in late September–October 2004, occurs more specifically in the Southeastern Africa-Madagascar region. The very good correlation of CH3OH and HCOOH with CO suggests that, despite the dominance of the biogenic source of these compounds on the global scale, biomass burning is their major source at Reunion Island between August and November.