Among typical range-free localization schemes for sensor networks, DV-Hop has its distinguishing advantage of the capability to localize unknown nodes, which have less than three or even no neighbor anchors. However, existing DV-Hop based localization methods have not considered the problem of packet collisions, which can frequently happen during the throughout-whole-network broadcast of numerous data packets at the first two steps of DV-Hop. In order to effectively improve the success rate of packet transmission between nodes, this paper proposes a medium access control (MAC) method based on Chinese Remainder Theorem (CRT) protocol sequence for DV-Hop localization. First, a broadcasting strategy is designed for the proposed MAC method. Then, dedicated procedures for both anchor nodes and unknown nodes are presented to implement the designed MAC method in DV-Hop localization. Through simulation and evaluation, the performance of DV-Hop localization with the proposed MAC method is thoroughly investigated. Simulation results show that when the number of protocol sequences is larger than a certain number, the proposed MAC method can provide DV-Hop with better localization accuracy than E-CSMA/CA, while keeping similar localization time.