This study investigated the non-equilibrium hydrogen absorption reaction paths of the AB5-type LaNi2Co3 alloy using time-resolved in situ synchrotron X-ray diffraction. Diffraction data were collected every second for reactions under two hydrogen loading pressures. Hydrogen absorption with a hydrogen loading of 1 MPa rapidly transformed α phase to a transient phase (estimated to be LaNi2Co3H3.1–3.6, named γ∗); this has not previously been observed under equilibrium processes. The γ∗ phase continuously transformed into the γ phase (LaNi2Co3H4.5–5.0), and the β phase (LaNi2Co3H~3.6) was not formed. When 0.18 MPa of hydrogen was loaded, initially, the γ∗ phase appeared, followed by the formation of the β phase, finally transforming into the γ phase. These results indicate that a higher loading pressure promotes the formation of the γ∗ phase and assists its continuous transformation into the γ phase by enhancing the dissolution of hydrogen into the α and γ∗ phases. Display omitted •Hydrogen absorption processes were observed every second in real time.•Reaction paths via a new transient phase were found.•Fast and slow reactions followed different reaction paths.•The lattice expansion was discussed in relation to the hydrogen distribution.