The need for decarbonization has inspired the utilization of methanol in transportation industry. Via both experimental and modeling frameworks, this study, for the first time, reveals the ignition, heat release and flame development characteristics of methanol mixed with different cetane improvers, i.e., 2-ethylhexyl nitrate (EHN) and di-tertiary‑butyl peroxide (DTBP), under practical, advanced engine conditions. Particularly, a detailed chemical kinetic model is newly developed for methanol/EHN/DTBP mixtures, incorporating the most updated sub-chemistries for relevant fuel components and critical intermediates, to assist in further analysis on the effects of EHN and DTBP on ignition and emission formation under engine thermodynamic environments derived from recorded in-cylinder pressure histories. Results show that stable combustion of methanol/EHN mixtures can be realized under low direct injection (DI) pressure, high in-cylinder thermodynamic condition, featuring the lowest coefficient of variation of indicated mean effective pressure (COVIMEP) of 1.46 %. Throughout the combustion process, the yellow and white flame dominates. At the same DI timing, methanol/EHN mixtures present shorter ignition delay, faster heat release rate (HRR) and more advanced combustion phasing compared with methanol/DTBP mixtures. At similar combustion phasing, the peak flame/OH* natural luminosity intensity of methanol/EHN mixtures is higher. KL factor, which is utilized to evaluate soot concentration, also shows similar trend, indicating higher sooting tendency of methanol/EHN mixtures. Flux analysis further highlights higher production of soot precursor (i.e., C2H2) with EHN than DTBP, primarily via the pathway of C2H4→ C2H3→C2H2. The active atmosphere created by the decomposition of EHN or DTBP has significant effects on decreasing methanol ignition delay in the early stage of their exothermic process, while the active atmosphere of EHN remains impactful whereas that of DTBP diminishes at later stages. The thermal atmosphere shows greater effects on methanol ignition at later stages of the exothermic process of EHN or DTBP decomposition than the early stages.