Virtual reality (VR) technology has received considerable attention over the last few years, with applications in many performance domains including training of sports-related mental and motor skills. The exact psychological and neurobiological mechanisms underlying potential VR training effects in athletes, however, remain largely unknown. The present longitudinal functional magnetic resonance imaging (fMRI) case study reports behavioral and neuroanatomical effects of VR soccer (a.k.a. football) heading training in a male adult amateur player. The study was conducted over 8 weeks, starting with a pre-test, followed by a 4-week VR training phase, during which weekly fMRI assessments and the first behavioral post-test were conducted. After an additional 4-week retention phase, the final fMRI assessment and the second behavioral post-test were conducted. Substantial improvement in real-life heading performance was accompanied by both structural and functional neuroanatomical changes. The comparison of the T1-weighted images revealed an increase in GM volume in the left thalamus and an increase in WM volume in the bilateral cerebellum. Furthermore, the analysis of the surface images showed an increase in cortical thickness in the right insula, left inferior temporal gyrus, left parahippocampal gyrus, left lingual gyrus, left posterior cingulate cortex, and bilateral anterior cingulate and medial prefrontal cortex. The seed-based correlation analyses of the resting-state fMRI data revealed manifold increases in functional connectivity within and between important brain networks. This study contributes to the growing literature on VR training in athletes and provides the world's first evidence on fundamental neurobiological mechanisms underlying neuroplasticity related to VR training effects in sports.