Methanol/high reactivity fuel (HRF) dual fuel combustion cannot further extend methanol energy ratio (MER) at medium and low loads. Polyoxymethylene dimethyl ether (PODE) as a biofuel with high cetane number is well suited for HRF. This paper explored the effect of spark ignition (SI) on energy conversion and MER extension for methanol/PODE under medium and low loads. The results show that SI triggers the exothermic processes of SI and dual fuel spark-assisted compression ignition (D-SACI). SI raised MER from 30 %, 40 %, 46 % to 40 %, 60 %, 90 % for brake mean effective pressure (BMEP) of 0.2, 0.4, 0.6 MPa, respectively. SI and D-SACI combustion can partially or completely replace premixed compression ignition (CI). Diffusion combustion and one or more exothermic processes of SI, D-SACI and premixed CI make up two-stage or three-stage exotherm. D-SACI is easily triggered when spark timing approaches PODE injection timing, otherwise, SI exotherm is easily triggered; at BMEP of 0.6 MPa, the exothermic energy of premixed CI is gradually converted into the exothermic energy of D-SACI and SI as MER increases. By optimizing, maximum brake thermal efficiency for BMEP of 0.4 and 0.6 MPa are 37.75 % and 42.82 %, respectively, corresponding to the MER of 50 % and 80 %, respectively.