In fire safety engineering, the use of computational fluid dynamics (CFD) allows for detailed multidimensional calculations of important parameters, for example, temperature. However, increasing use of CFD models puts requirements on experimental validation, a challenge for many measurement techniques under harsh fire conditions. In this work, laser-based picosecond light detection and ranging (ps-lidar) was used for remote measurements in a 1/2-scale ISO 9705 room containing either a methanol pool fire or a methane diffusion flame. Spatially resolved Rayleigh thermometry was conducted in the vertical door plane and in a horizontal plane inside the room. Temperatures obtained by ps-lidar are compared with values from thermocouples located in the doorway as well as results from CFD simulations. The technique allows for quantitative thermometry provided that minimal particle scattering interferences are present. Measurements of detailed distributions of temperature and particulates clearly demonstrate the potential of ps-lidar for diagnostics in large-scale combustion.