The femtosecond response of NO-doped rare gas matrices is studied within a stochastic Langevin theoretical framework. As is shown, a simple damped harmonic oscillator model can describe properly the absorption and emission line shapes associated with the NO (A(2)Sigma(+) <-> X-2 Pi) electronic transitions inside these media as well as the matrix first solvation shell response in a process with two timescales, finding a fairly good agreement with available experimental data. This approach thus constitutes an alternative and complementary way to analyze the structural relaxation dynamics of systems in liquids and solids, leading to a better understanding of the underlying physics. (C) 2009 Elsevier B.V. All rights reserved.