Large Eddy Simulation of knocking in piston engines requires high-fidelity physical models and numerical techniques. The need to capture temperature fields with high precision to predict autoignition is an additional critical constraint compared to existing LES in engines. The present work presents advances for LES of knocking in two fields: (1) a Conjugate Heat Transfer (CHT) technique is implemented to compute the flow within the engine over successive cycles with LES together with the temperature field within the cylinder head walls and the valves and (2) a reduced two-step scheme is used to predict both propagating premixed flames as well as autoignition times over a wide range of equivalence ratios, pressures and temperatures. The paper focuses on CHT which is critical for knocking because the gas temperature field is controlled by the wall temperature field and knocking is sensitive to small temperature changes. The CHT LES is compared to classical LES where the temperatures of the head and the valves are supposed to be homogeneous and imposed empirically. Results show that the skin temperature field (which is a result of the CHT LES while it is a user input for classical LES) is complex and controls knocking events. While the results of the CHT LES are obviously better because they suppress a large part of the empirical specification of the wall temperatures, this study also reveals a difficult and crucial element of the CHT approach: the description of exhaust valves cooling which are in contact with the engine head for part of the cycle and not in the rest of the cycle, leading to difficulties for heat transfer descriptions between valves and head. The CHT method is successfully applied to an engine studied at IFP Energies Nouvelles where knocking characteristics have been studied over a wide range of conditions.