The reasons behind the occurrence of a second/end peak heat release rate (PHRR) during wood combustion under radiative heating were determined. Effects of the type of rear material, wood thickness, char progression, and its microstructure, as well as moisture content/transport in spruce wood, were studied. Rear materials used were insulating Kaowool, conducting steel, and the same wood but physically separated from test specimen by aluminium foil. The intensity of the second/end PHRR with Kaowool was almost 50% more than that of the sample with steel. Thus, the second/end peak is governed by the boundary condition defined by the rear material, which determines the heat losses at the rear side of the specimen and consequently the temperature of the specimen. Higher specimen temperature enhances the pyrolysis rate, thereby causing the second/end PHRR. The appearance times and values of the second/end PHRR for 30, 20, and 10 mm wood were 1740 s/78 kWm−2, 685 s/134 kWm−2, and 450 s/160 kWm−2, respectively. Char progressed to the rear of the samples even with a thin (8 mm) conductive steel substrate. Cracks in char grew almost three times wider during the second/end PHRR compared to the sample with no second/end peak. Char cracking had no significance on the time of occurrence of the second/end PHRR but affected the overall heat release. High moisture content reduced the charring rate and delayed the time of occurrence of the second/end PHRR as more water was needed to undergo a phase change, requiring a higher amount of energy.