Flammability properties of solid materials are necessary to be a known parameter for many purposes: among them, forensic investigations of fire and explosion events, fire risk or hazard analysis, design and development of combustion-based systems. However, despite the large quantity of data in the literature, the flammability properties of many materials still appear not to be available or show a degree of uncertainty associated with them, which makes their value limited. The present work is aimed at proposing a calorimetric-based approach to determine some flammability and thermophysical properties of solids, with specific regard to time-to-ignition as a function of the imposed heat flux. Plastic materials have been here chosen as test cases, even though this approach has a general applicability. The two mentioned parameters have been analyzed to provide a quantitative estimation of the critical heat flux (minimum heat flux resulting in ignition). A cone calorimeter has been employed to conduct the experiments: the facility complies with standard ASTM E 1354; the related uncertainty and validity range has been evaluated through an appropriate error analysis. Finally, thermal inertia has been thereby calculated for the considered materials through a simple thermodynamic model, which is based upon critical heat flux and energy conservation.