Abstract The kinetics and mechanisms of selective maltose hydrogenation over Raney Ni remain poorly understood, which hinders the industrial advancement of maltitol production for biorefining. Herein, the impact of hydrogenation conditions and in‐depth mechanistic characterizations were carefully investigated in this research. Optimization of reaction conditions illustrated that maltitol formation was favored by moderate reaction temperatures (≤130°C), high hydrogen pressures (>7 MPa), and near‐neutral sodium phosphate buffer (pH = 6.47). Kinetic studies demonstrated the E a of 45.5 kJ/mol for the hydrogenation of maltose. The in situ IR revealed that the hydrogenation of maltose over Raney Ni occurs in the order of ring opening and adsorption via CO of the aldose form followed by hydrogenation. The UV–vis spectra demonstrated the near‐neutral setting (pH = 6.47) promoted the production of open‐chain aldose conformation and selective CO hydrogenation to the corresponding alcohols. The present study on concentrated‐maltose hydrogenation paves the way for the industrial development of maltitol manufacturing.