With the increasing global concern over climate change, reducing greenhouse gas emissions has become a universal goal for governments and enterprises. For oversize and heavyweight cargo (OHC) transportation, multimodal transportation has become widely adopted. However, this mode inevitably generates carbon emissions, making research into effective emission reduction strategies essential for achieving low-carbon economic development. This study investigates the optimization of multimodal transportation paths for OHC (OMTP-OHC), considering various direct carbon pricing policies and develops models for these paths under the ordinary scenario—defined as scenarios without any carbon pricing policies—and two carbon pricing policy scenarios, namely the emission trading scheme (ETS) policy and the carbon tax policy, to identify the most cost-effective solutions. An enhanced genetic algorithm incorporating elite strategy and catastrophe theory is employed to solve the models under the three scenarios. Subsequently, we examine the impact of ETS policy price fluctuations, carbon quota factors, and different carbon tax levels on decision-making through a case study, confirming the feasibility of the proposed model and algorithm. The findings indicate that the proposed algorithm effectively addresses this problem. Moreover, the algorithm demonstrates a small impact of ETS policy price fluctuations on outcomes and a slightly low sensitivity to carbon quota factors. This may be attributed to the relatively low ETS policy prices and the characteristics of OHC, where transportation and modification costs are significantly higher than carbon emission costs. Additionally, a comparative analysis of the two carbon pricing policies demonstrates the varying intensities of emission reductions in multimodal transportation, with the ranking of carbon emission reduction intensity as follows: upper-intermediate level of carbon tax > intermediate level of carbon tax > lower-intermediate level of carbon tax = ETS policy > the ordinary scenario. The emission reduction at the lower-intermediate carbon tax level (USD 8.40/t) matches that of the ETS policy at 30%, with a 49.59% greater reduction at the intermediate level (USD 50.48/t) compared to the ordinary scenario, and a 70.07% reduction at the upper-intermediate level (USD 91.14/t). The model and algorithm proposed in this study can provide scientific and technical support to realize the low-carbonization of the multimodal transportation for OHC. The findings of this study also provide scientific evidence for understanding the situation of multimodal transportation for OHC under China’s ETS policy and its performance under different carbon tax levels in China and other regions. This also contributes to achieving the goal of low-carbon economic development.