Human factors play an indispensable role in process safety during fire risk process. Fire evacuation of underground comprehensive buildings is a critical consideration for practical importance. Here, evacuation experiments were conducted in the Guangzhou East Railway Station Plaza, a large underground comprehensive building in Guangdong, China, with the plaza occupants as the participants. The evacuation factors, namely evacuation time and evacuee-selected evacuation routes, were evaluated using empirical equations (the Togawa model and the Melinek and Booth model) and evacuation modelling software (EVACNET 4 and composite occupant evacuation model). The experimental data were used to verify the empirical equations and evacuation models and to modify specific empirical parameters. The effect on escape route judgement and selection under emergency situations was analysed. The results demonstrated that direct access to outdoor exits could considerably reduce evacuation time. The experimental N and ts were 1 person/m·s and 28 s, respectively. The total evacuation time was 281 s, and the EVACNET 4 and composite models’ simulations of safe evacuation were 285–290 s, which was consistent with the experimental data—validating the high accuracy and applicability of the models.