Global positioning system (GPS) technology is well suited for attitude determination. However, in land vehicle application, low-cost single frequency GPS receivers which have low measurement quality are often used, and external factors such as multipath and low satellite visibility in the densely built-up urban environment further degrade the quality of the GPS measurements. Due to the low-quality receivers used and the challenging urban environment, the success rate of the single epoch ambiguity resolution for dynamic attitude determination is usually quite low. In this paper, a micro-electro-mechanical system (MEMS)—inertial navigation system (INS)-aided ambiguity resolution method is proposed to improve the GPS attitude determination performance, which is particularly suitable for land vehicle attitude determination. First, the INS calculated baseline vector is augmented with the GPS carrier phase and code measurements. This improves the ambiguity dilution of precision (ADOP), resulting in better quality of the unconstrained float solution. Second, the undesirable float solutions caused by large measurement errors are further filtered and replaced using the INS-aided ambiguity function method (AFM). The fixed solutions are then obtained by the constrained least squares ambiguity decorrelation (CLAMBDA) algorithm. Finally, the GPS/MEMS-INS integration is realized by the use of a Kalman filter. Theoretical analysis of the ADOP is given and experimental results demonstrate that our proposed method can significantly improve the quality of the float ambiguity solution, leading to high success rate and better accuracy of attitude determination.