The special large-slope V-shaped structure of underwater tunnels changes the ventilation characteristics during tunnel construction, making the traditional experience limited. Therefore, it is urgent to study the influence of the special structure on the safety of the air environment during construction. In this paper, a series of small-scale experiments were conducted to investigate the ventilation characteristics of V-shaped tunnels. The coupled effects of ventilation parameters (distance of duct outlet from working face Lo, air velocity at the duct outlet uo) and structural characteristics (digging length Ld, slope of the uphill section q) were considered. The extreme slope of the V-shaped tunnel of 8% was considered. The flow field and pollutant transport law were determined by using CO as a tracer in the experiments. The results show that uo has a positive impact on the air return velocity, while Ld has a negative impact, and neither of the other two factors has a significant effect. The transport characteristics of CO in V-shaped tunnels differ from those in flat tunnels, with the former tending to cause unconventional areas of high pollutant concentrations in the horizontal sections. Furthermore, the correlations between CO concentration and distance, ventilation time, and the influence factors discussed in this paper are derived from the experimental results. The conclusions provide guidance for the construction of V-shaped tunnels to prevent air pollution in the construction environment and to improve the working conditions of laborers. Additionally, it can also enrich the ventilation experience in tunnel construction.