Urban rail transit trips usually involve multiple stages, which can be differentiated in terms of transfers that may involve distinct access and egress modes. Most studies on access and egress mode choices of urban rail transit have separately examined the two mode choices. However, in reality, the two choices are temporally correlated. This study, therefore, has sequentially applied the mixed logit to examine the contributors of access and egress mode choices of urban metro commuters using the data from a recent survey conducted in Nanjing, China. 9 typical multimodal combinations constituted by 5 main access modes (walk, bike, electric bike, bus, and car) and 2 main egress modes (walk and bus) are included in the study. The result proves that the model is reliable and reproductive in analyzing access/egress mode choices of metro commuters. Estimation results prove the existence of time constraint and service satisfaction effect of access trip on commuters’ egress mode choice and reveal the importance of transfer infrastructure and environments that serve for biking, walking, bus riding, and car parking in commuter’s connection choice. Also, policy implications are segmentally concluded for the transfer needs of commuters in different groups to encourage the use of metro multimodal trips.