Four different expressions, derived from the diffusion theory or the random walk model, were used to fit time‐resolved reflectance data for the evaluation of tissue optical properties. The experimental reflectance curves were obtained from phantoms of known optical parameters (absorption and transport scattering coefficients) covering the range of typical values for biological tissues between 600 and 900 nm. The measurements were performed using an instrumentation for time‐correlated single‐photon counting. The potential of the four methods in the assessment of the absorption and transport scattering coefficients was evaluated in terms of absolute error, linearity error, and dispersion of data. Each method showed different performances depending on the optical properties of the sample and the experimental conditions. We propose some criteria for the optimal choice of the fitting method to be used in different applications.