Ammonia (NH3), as an ideal zero-carbon fuel, plays a positive role in mitigating global warming. By cofiring NH3 with highly reactive small molecule fuels such as hydrogen (H2), carbon monoxide (CO) and methane (CH4), the reactivity of NH3 combustion can be significantly enhanced. In this work, a detailed kinetic mechanism for NH3/CH4/H2/CO containing 146 species and 1099 reactions was developed and extensively validated with selected experimental data from the literature on laminar burning velocity (LBV), ignition delay time (IDT), and species concentrations measured in burner-stabilized flames (BSF), plug flow reactors (PFR) and jet-stirred reactors (JSR), covering temperatures of 273–2000 K, pressures of 0.053–40 atm and equivalence ratios of 0.1–2. In addition, the detailed mechanism was simplified to include 53 species and 353 reactions using three simplification methods. Kinetic modeling analysis showed that the chemical and transport effects of H2, CO and CH4 are the main factors enhancing NH3 combustion, which rising with the increasing initial temperature and decreasing ammonia blending ratio. Among the four reactants, H2 is consumed first, followed by CH4 and NH3, with CO reacting last. By modifying the Metghalchi-Kech power law equation, it was found that a clear linear relationship exists between LBV and the sum of the maximum mole fractions of O, H, OH, and NH2 radicals.