Biogas has been a promising alternative fuel for IC engines. However, its CO2 content reduces calorific value and ignitability. The CO2 fraction of raw biogas can be separated out by various techniques, which are collectively called methane enrichment. The present study explores the effect of methane enrichment on the output parameters of a Homogeneous Charge Compression Ignition (HCCI) engine. A single cylinder CI engine is altered for this purpose. Biogas (CH4 + CO2) is supplied along with air. Diethyl Ether (DEE) is used as the secondary fuel to initiate auto-ignition. The effects of injecting DEE at the inlet port and upstream in the intake manifold are also compared. Performance, emission and combustion characteristics such as brake thermal efficiency, equivalence ratio, HC, CO, CO2, NOx and smoke emissions, start and duration of combustion, in-cylinder pressure and maximum heat release rate are compared for operation with raw biogas (50% methane) and methane enriched biogas (100% methane) for various biogas flow rates and engine torques. Results show that methane enrichment enhances brake thermal efficiency by up to 2% compared to raw biogas. Methane enrichment advances and speeds up combustion. HC, CO and CO2 emissions, maximum cylinder pressure and maximum heat release rate are also improved with methane enrichment. Ultra-low NOx and smoke emissions can be obtained using raw biogas as well as methane enriched biogas. Low biogas flow rates provide better brake thermal efficiency and HC emissions. Manifold injection of DEE enhances brake thermal efficiency by up to 2% compared to port injection by virtue of greater mixture homogeneity. © 2021 Hydrogen Energy Publications LLC