The probability of structural ignition is dependent both on physical properties of materials and the fire exposure conditions. In this study, the effect of firebrand characteristics (i.e., firebrand size, number of firebrands) on wood ignition behavior was considered. Mathematical modeling and laboratory experiment were conducted to better understand the conditions of wood ignition by a single or group of firebrands with different geometry. This model considers the heat exchange between the firebrands, wood layer and the gas phase, moisture evaporation in the firebrands and the diffusion gases of water vapor in the pyrolysis zone. In order to test and verify the model, a series of experiments to determine probability and conditions for ignition of wood-based materials (plywood, oriented strand board, chipboard) caused by wildland firebrands (pine twigs with a diameter of 6–8 mm and a length of 40 ± 2 mm) were conducted. The experiments investigated the firebrand impact on the wood layer under different parameters, such as firebrand size and quantity, wind speed, and type of wood. The results of experiments showed that the increase in wind speed leads to the increase in probability of wood ignition. Based on the received results, it can be concluded that the ignition curve of wood samples by firebrands is nonlinear and depends on the wind speed and firebrand size as well as their quantity. At the same time, there is no ignition of wood samples in the range of wind speed of 0–1 m/s. The ignition of wood is possible with a decrease in the distance between the firebrands with a decrease in the firebrand length. This result agrees more closely with the model.