Oximes and related derivatives featuring a CN double bond are important in many areas of chemistry. Different methods for the determination of the E/Z configuration have been developed, each with its own scope and limitations. While some cannot be used when only one isomer is available, others require special NMR experiments. Here, three popular computational methodologies (DP4, DP4+, and ML-J-DP4) have been thoroughly studied using a challenging test set. Although DP4+ provides the best confidence, its computational cost might be high. On the other hand, ML-J-DP4 shows excellent performance in most cases in a fraction of CPU time. A detailed analysis of the structural factors affecting the NMR prediction and sense of the assignment is also provided.