The self-acceleration of spherically expanding flames were investigated using a constant volume combustion chamber for CO/H2/O2/N2 mixtures over a wide range of initial pressure from 0.2 to 0.6 MPa, CO/H2 ratio from 50/50 to 10/90 and equivalence ratio from 0.4 to 1.5. The adiabatic flame temperature was kept constant by adjusting O2/N2 ratio at different equivalence ratios. Schlieren images were recorded to investigate the flame front evolution of spherically expanding flames. Local acceleration exponents were extracted using a proper equation to study the process of flame self-acceleration. Results show that the flame cells develop on the smooth flame fronts and finally reach fractal-like structures due to the hydrodynamic and diffusional-thermal instabilities, resulting in flame self-accelerative propagation. The critical Peclet number corresponding to the onset of self-acceleration, Pecr increases nonlinearly with the Markstein length, Ma. The observation further reveals that the onset of self-acceleration is mainly controlled by the diffusional-thermal effect. There exists two distinct flame propagation regimes in the self-acceleration, namely quick transition accelerative and quasi self-similar accelerative regimes. The quick transition regime is controlled by the destabilization effect of hydrodynamic perturbation and stabilization effect of flame stretch. While the quasi self-similar regime is primarily affected by the cascading process of flame front cells controlled by hydrodynamic instability. The self-similar acceleration exponent, αs varies with the initial pressure and Lewis number, Le. The values of αs are measured to be 1.1–1.25 (smaller than 1.5), indicating the flame dose not attain self-turbulization. •Effects of intrinsic instability on flame front evolution were investigated systematically.•Three distinct regimes in flame propagation were observed and analyzed in detail.•Critical onset and transition Peclet numbers in flame self-acceleration were obtained.•Accurate self-similar acceleration exponent of syngas flames was measured.