A pore-array intensified tube-in-tube microchannel (PA-TMC), which is characterized by high throughput and low pressure drop, was developed as a gas–liquid contactor. The sulfite oxidation method was used to determine the oxygen efficiency (φ) and volumetric mass transfer coefficient (k_La) of PA-TMC, and the mass transfer amount per unit energy (ε) was calculated by using the pressure drop. The effects of structural and operating parameters were investigated systematically, and the two-phase flow behavior was monitored by using a charge-coupled device imaging system. The results indicated that the gas absorption efficiency and mass transfer performance of the PA-TMC were improved with increasing pore number, flow rate, and number of helical coil turns and decreasing pore size, row number, annular size, annular length, and surface tension. The φ, ε and k_La of PA-TMC could reach 31.3%, 1.73 × 10⁻⁴ mol/J, and 7.0 s⁻¹, respectively. The Sherwood number was correlated with the investigated parameters to guide the design of PA-TMC in gas absorption and mass transfer processes.