Ignition and flame spread theory is fundamental for evaluating the risk posed by a material during the early stages of a fire. This paper presents an experimental investigation aimed at understanding the parameters which govern the ignition of solids exposed to transient irradiation. Emphasis is placed on the conditions at ignition, including an energy balance to describe surface phenomena and the link between gas phase and solid phase processes. Experiments were performed in a fire calorimetry apparatus and incorporated a gas analysis system to study gas phase composition. Samples of Polyamide 6 (PA6) measuring 85 × 85 × 20 mm were used. Experiments were carried out to independently measure temperature in the solid phase and mass loss rate (MLR) over time. The MLR at ignition was calculated to be between 2.0 and 6.0 g/(m2 s) for all but 3 experiments, were outliers presented values of 7.9, 10.7 and 14.4 g/(m2 s). Temperature was recorded through the thickness of the solid, at depths of 4, 8, 12 and 16 mm from the surface. A regression analysis was used to calculate the surface temperature at ignition for all experiments, and it was found to vary between 270 and 325 °C for all but one experiment, were a temperature of 402 °C was recorded. The temperature distribution in the solid phase was used to estimate the net absorbed heat flux at the surface by applying Fourier’s law; with values ranging between 2.0 and 9.8 kW/m2. From the gas analysis, it was possible to assess the identity, mass flux and concentration of three dominant species produced before ignition: carbon monoxide, methane and hexane. These results are of value for the physical modelling of ignition and flame spread phenomena, allowing for more accurate criteria to describe the onset of ignition under a range of heating conditions.