The binary fuel blend of H2/CH4 is one of the most promising hydrogen-enriched hydrocarbon fuels in spark-ignition (SI) engines. Yet, the undesirable phenomenon of super-knock, which can severely and instantaneously damage an SI engine, limits its widespread adoption. Moreover, there is still a lack of consensus on the precise mechanism by which this phenomenon occurs i.e. via flame acceleration or spontaneous ignition, despite numerous previous investigations. At the same time, recent studies [M. P. Burke, S. J. Klippenstein, Nat. Chem. 9 (2017) 1078 - 1082, Y. Tao, A. W. Jasper, Y. Georgievskii, S. J. Klippenstein, R. Sivaramakrishnan, Proc. Combust. Inst. 38 (2021) 515–522] have demonstrated a high probability of occurrence of non-thermal reactions in premixed flames of such H2/CH4 fuel blends with air due to the presence of non-trivial amounts of highly reactive radicals including H, O and OH apart from O2. The present study focuses on the evolution of an initial deflagration front to a detonation wave in H2/CH4-air mixtures under SI engine relevant conditions through fully resolved, constant volume 1D simulations with and without non-thermal reactivity. Non-thermal reactions were included in the macroscopic kinetics model as chemically termolecular reactions facilitated by the H + CH3 and H + OH radical-radical recombination and the H + O2 radical-molecule association reactions. The nonthermal reactions result in a corresponding decrease in the reaction fluxes of the incipient recombination/association reactions. Therefore, an additional set of simulations were performed by applying corrections to the respective incipient recombination/association rate constants using the methodology demonstrated by Tao et al. [Y. Tao, A. W. Jasper, Y. Georgievskii, S. J. Klippenstein, R. Sivaramakrishnan, Proc. Combust. Inst. 38 (2021) 515–522]. Compared to the baseline case, the onset of spontaneous ignition in the end-gas region was observed to be delayed in the presence of non-thermal termolecular reactions. Concurrently, the developing detonation was observed to be significantly stronger. In contrast, applying corrections to the recombination/association rate constants resulted in a completely different behavior. Specifically, detonation was observed to occur due to self acceleration of the primary flame in the absence of spontaneous ignition in the end-gas region. Sensitivity analysis was performed to quantify the effects of non-thermal reactions on the duration of heat release rate and thereby the mechanism of detonation formation. In addition, chemical explosive mode analysis (CEMA) was performed to identify the dominant species/reactions responsible for the observed results.