Hydrogen was recovered and purified from coal gasification-produced syngas using two kinds of hybrid processes: a pressure swing adsorption (PSA)-membrane system (a PSA unit followed by a membrane separation unit) and a membrane-PSA system (a membrane separation unit followed by a PSA unit). The PSA operational parameters were adjusted to control the product purity and the membrane operational parameters were adjusted to control the hydrogen recovery so that both a pure hydrogen product (>99.9%) and a high recovery (>90%) were obtained simultaneously. The hybrid hydrogen purification processes were simulated using HYSYS and the processes were evaluated in terms of hydrogen product purity and hydrogen recovery. For comparison, a PSA process and a membrane separation process were also used individually for hydrogen purification. Neither process alone produced high purity hydrogen with a high recovery. The PSA-membrane hybrid process produced hydrogen that was 99.98% pure with a recovery of 91.71%, whereas the membrane-PSA hybrid process produced hydrogen that was 99.99% pure with a recovery of 91.71%. The PSA-membrane hybrid process achieved higher total H recoveries than the membrane-PSA hybrid process under the same H recovery of membrane separation unit. Meanwhile, the membrane-PSA hybrid process achieved a higher total H recovery (97.06%) than PSA-membrane hybrid process (94.35%) at the same H concentration of PSA feed gas (62.57%).