Shifts in spatial attention are associated with variations in alpha-band (α, 8–14 Hz) activity, specifically in inter-hemispheric imbalance. The underlying mechanism is attributed to local α-synchronisation, which regulates local inhibition of neural excitability, as well as fronto-parietal synchronisation reflecting long-range communication. The direction-specific nature of this neural correlate brings forward its potential as a control signal in brain-computer interfaces (BCI). In the present study we explored whether long-range α-synchronisation presents lateralised patterns dependent on voluntary attention orienting, and whether these patterns can be picked up at single-trial level to provide a control signal for active BCI. We collected electroencephalography (EEG) data from a cohort of healthy adults (n = 10) while performing a covert visuospatial attention (CVSA) task. The data show lateralised patterns of α-band phase coupling between frontal and parieto-occipital regions after target presentation, replicating previous findings. This pattern, however, was not evident during the cue-target orienting interval, the ideal time window for BCI. Furthermore, decoding the direction of attention trial-by-trial from cue-locked synchronisation with support vector machine (SVM) was at chance level. The present findings suggest EEG may not be capable of detecting long-range α-synchronisation in attentional orienting on a single-trial basis, and, thus, highlight the limitations of this metric as a reliable signal for BCI control.