Non-orthogonal multiple access (NOMA) emerges as a promising candidate for 5G, which radically alters the way users share the spectrum. In the NOMA system, user clustering (UC) becomes another research issue as grouping the users on different subcarriers with different power levels has a significant impact on spectral utilization. In previous literature, plenty of works have been devoted to solving the UC problem. Recently, the artificial neural network (ANN) has gained considerable attention due to the availability of UC datasets, obtained from the Brute-Force search (BF-S) method. In this paper, deep neural network-based UC (DNN-UC) is employed to effectively characterize the nonlinearity between the cluster formation with channel diversity and transmission powers. Compared to the ANN-UC, the DNN-UC is more competent as UC is a non-convex NP-complete problem, which cannot be entirely captured by the ANN model. In this work, the DNN-UC is first trained with the training samples and then validated with the testing samples to examine its mean square error (MSE) and throughput performance in an asymmetrical fading NOMA channel. Unlike the ANN-UC, the DNN-UC model offers greater room for hyper-parameter optimizations to maximize its learning capability. With the optimized hyper-parameters, the DNN-UC can achieve near-optimal throughput performance, approximately 97% of the throughput of the BF-S method.