Bromine monoxide (BrO) is relevant to atmospheric oxidative capacity, affecting the lifetime of greenhouse gases (i.e., methane, dimethylsulfide) and mercury oxidation. However, measurements of BrO radical vertical profiles are rare, and BrO is highly variable. As a result, the few available aircraft observations in different regions of the atmosphere are not easily reconciled. Autonomous multi-axis differential optical absorption spectroscopy (MAX-DOAS) instruments placed at remote mountaintop observatories (MT-DOAS) present a cost-effective alternative to aircraft, with the potential to probe the climate-relevant yet understudied free troposphere more routinely. Here, we describe an innovative full-atmosphere BrO and formaldehyde (HCHO) profile retrieval algorithm using MT-DOAS measurements at Mauna Loa Observatory (MLO – 19.536° N, 155.577° W; 3401 m a.s.l.). The retrieval is based on time-dependent optimal estimation and simultaneously inverts 190+ individual BrO (and formaldehyde, HCHO) SCDs (slant column densities; SCD = dSCD + SCDRef) from solar stray light spectra measured in the zenith and off-axis geometries at high and low solar zenith angles (92° > SZA > 30°) to derive BrO concentration profiles from 1.9 to 35 km with 7.5 degrees of freedom (DoFs). Two case study days are characterized by the absence (26 April 2017, base case) and presence of a Rossby-wave-breaking double tropopause (29 April 2017, RW-DT case). Stratospheric-BrO vertical columns are nearly identical on both days (VCD = (1.5 ± 0.2) × 1013 molec. cm−2), and the stratospheric-BrO profile peaks at a lower altitude during the RW-DT (1.6–2.0 DoFs). Tropospheric-BrO VCDs increase from (0.70 ± 0.14) × 1013 molec. cm−2 (base case) to (1.00 ± 0.14) × 1013 molec. cm−2 (RW-DT) owing to a 3-fold increase in BrO in the upper troposphere (1.7–1.9 DoFs). BrO at MLO increases from (0.23 ± 0.03) pptv (base case) to (0.46 ± 0.03) pptv (RW-DT) and is characterized by an added time resolution (∼ 3.8 DoFs). Up to (0.9 ± 0.1) pptv BrO is observed above MLO in the lower free troposphere in the absence of the double tropopause. We validate the retrieval using aircraft BrO profiles and in situ HCHO measurements aboard the NSF/NCAR GV aircraft above MLO (11 January 2014) that establish BrO peaks around 2.4 pptv above 13 km in the upper troposphere–lower stratosphere (UTLS) during a similar RW-DT event (0.83 × 1013 molec. cm2 tropospheric-BrO VCD above 2 km). The tropospheric-BrO profile measured using MT-DOAS (RW-DT case) and using the aircraft agree well (after averaging-kernel smoothing). Furthermore, these tropospheric-BrO profiles over the central Pacific Ocean are found to closely resemble those over the eastern Pacific Ocean (2–14 km) and are in contrast to those over the western Pacific Ocean, where a C-shaped tropospheric-BrO profile shape has been observed.