Heart rate variability (HRV) has the potential to be a predicting factor of cognitive performance. The present research aimed to explore the differences in neurocognitive performance of workers with high HRV and low HRV. A total of 48 white-collar workers and 53 blue-collar workers were assessed. An electrocardiogram was used to obtain HRV data, whereby a 10 min baseline and an active (neuropsychological task) recording were taken. Median splits were performed on data to obtain high- and low-HRV groups. The Cambridge Neuropsychological Test Automated Battery, specifically, the spatial working memory, attention-switching task, rapid visual processing, and spatial span were used. Higher HRV (RMSSD and HF) was linked to better neurocognitive performance measures. Interestingly, the blue- and white-collar groups exhibited different correlations and, in some cases, showed an inverse relationship with the same variables. The differences observed in the present study demonstrate the importance of assessing task-dependent HRV parameters.