Mixing length scales for methane–oxygen shear-coaxial single-element rocket injectors were experimentally assessed using laser absorption tomography. The laser spectroscopy technique enables quantitative and spatially resolved measurements of carbon monoxide (CO) and temperature within the near-field region, probing rovibrational absorption lines of CO near 5 μm. Multiple injector designs were examined with differing oxidizer post recess depths to compare mixing characteristics. All tests were performed at an oxidizer-to-fuel ratio of 3 with a total propellant flow rate of 0.350 g/s. Planar measurements were taken at 16 axial positions, which collectively captured the first 57 mm of each flame. A tomographic inversion method was applied to obtain radially resolved distributions of temperature and CO mole fraction for each axial position, from which two-dimensional images of the thermochemical structure were generated. Characteristic mixing parameters are defined and extracted from features within the species and temperature profiles to visualize the spatial evolution of CO production. Increasing oxidizer post recess improved mixing due to enhanced shear-induced turbulence and associated radial diffusion of species and temperature; however, the enhancement was nonlinear. This work establishes the first use of laser absorption tomography to directly measure mixing length scales associated with temperature and species profiles in coaxial flames.