Background. A rich vocabulary supports human achievements in socio-economic activities, education, and communication. It is therefore important to clarify the nature of language acquisition as a complex multidimensional process. However, both the psychological and neurophysiological mechanisms underpinning language learning, as well as the links between them, are still poorly understood. Objective. This study aims to explore the psychological and neurophysiological correlates of successful word acquisition in a person’s native language. Design. Thirty adults read sentences with novel nouns, following which the participants’ electroencephalograms were recorded during a word-reading task. Event-related potentials in response to novel words and alpha oscillation parameters (amplitude, variability, and long-range temporal correlation dynamics) were analyzed. Learning outcomes were assessed at the lexical and semantic levels. Psychological variables measured using Amthauer’s test (verbal abilities), BIS/BAS scales (motivation), and the MSTAT-1 (ambiguity tolerance) and alpha oscillation parameters were factored. Results. Better recognition of novel words was related to two factors which had high factor loadings for all measured alpha oscillation parameters, indicating the role of attention networks and respective neural activity for enabling information processing. More successful learners had lower P200 amplitude, which also suggests higher attention-system involvement. Another factor predicted better acquisition of word meanings for less ambiguity-tolerant students, while the factor which pooled logical conceptual thinking ability and persistence in goal-reaching, positively correlated with acquisition of both word forms and meanings. Conclusion. The psychological factors predominantly correlated with word-learning success in semantic tasks, while neurophysiological variables were linked to performance in the recognition task.