This paper presents data on widespread abnormal accumulations in coal deposits of some rare metal(loid)s (Ge, Ga, Se, Li and REE+Y), which play a key role in energy-efficient technologies and alternative power development. It is shown that enrichment of these metal(loid)s may occur in coal seams in host- and basement-rocks of coal basins at comparable concentrations to those in conventional ores. Genesis of high concentrations of the rare metal(loid)s and their modes of occurrence in coal basins are reviewed. Moreover, utilization prospects of these metal(loid)s as byproduct coal deposits are evaluated. The extraction of these metal(loid) resources during coal exploitation and utilization would not only increase beneficial use of coal deposits themselves but also promote humanity’s further movement on the “green road”.