In this work, we reported for the first time the effect of butanol isomerization on the photothermal production of hydrogen in the presence of a noble, metal-free Ti@TiO$_2$ core-shell photocatalyst. The experiments were performed in aqueous solutions of 1-BuOH, 2-BuOH, and t-BuOH under Xe lamp irradiation (vis/NIR: 8.4 W, UV: 0.6 W) at 35–69 °C. The increase in temperature significantly enhanced H$_2$ formation, indicating a strong photothermal effect in the studied systems. However, in dark conditions, H$_2$ emission was not observed even at elevated temperatures, which clearly points out the photonic origin of H$_2$ photothermal formation. The rate of H2 production followed the order of 1-BuOH >> 2-BuOH > t-BuOH in the entire range of studied temperatures. In the systems with 1-BuOH and 2-BuOH, hydrogen was the only gaseous product measured online in the outlet carrier argon using mass spectrometry. By contrast, a mixture of H$_2$, CH$_4$, and C$_2$H$_6$ was detected for t-BuOH, indicating a C–C bond scission with this isomer during photocatalytic degradation. The apparent activation energies, Ea, with 1-BuOH/2-BuOH isomers (20–21 kJ·mol−1) was found to be larger than for t-BuOH (13 kJ·mol$^{−1}$). The significant difference in thermal response for 1-BuOH/2-BuOH and t-BuOH isomers was ascribed to the difference in the photocatalytic mechanisms of these species. The photothermal effect with 1-BuOH/2-BuOH isomers can be explained by the thermally induced transfer of photogenerated, shallowly trapped electron holes to highly reactive free holes at the surface of TiO$_2$ and the further hole-mediated cleavage of the O-H bond. In the system with t-BuOH, another mechanism could also contribute to the overall process through hydrogen abstraction from the C–H bond by an intermediate •OH radical, leading to CH$_3$• group ejection. Formation of •OH radicals during light irradiation of Ti@TiO$_2$ nanoparticle suspension in water has been confirmed using terephthalate dosimetry. This analysis also revealed a positive temperature response of •OH radical formation.