Exploration of secondary resources for isolation of valuable constituents, such as rare earth elements (REEs) and trace elements (TEs), is of importance owing to the need to identify new domestic sources and reduce reliance on imports. The present study systematically discusses the distribution of REEs and TEs in core samples from the coal block of Bhalukasba Surni {(B1(125 m)-B9 (409 m)} located in Rajmahal coalfield, Jharkhand, India, which has not been investigated previously for its geochemistry. The studied coal samples were found to be enriched in TEs whose abundances were in the order of Mn > Mo > Zr > Ni > Cr > V > Cu > Zn > Pb, and REEs (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Tm, Yb, Lu) along with Sc and Y. The average concentration of REEs with yttrium (ΣREY) on an ash basis was 528 ppm, which is significantly higher than the world average for coal ash (435 ppm). Of the samples investigated, B3 (182–184 m) and B8 (396–399 m) demonstrated relatively higher concentrations of potentially economic elements, with B3 containing a higher proportion of middle to heavy REEs Gd, Dy, Ho and Er, and B8 showing relative enrichment in Nd and Y. On dry whole coal basis, B6 (275–278 m) showed a considerably higher concentration of Ge (55 ppm) than other samples, whereas the concentration of Zr varied in the range of 90–160 ppm in the whole coal block. X-ray diffraction studies revealed the presence of quartz, keatite, hematite, zircon, anatase and orthoclase in the coal ash samples prepared at 815 °C. REEs exhibited prominent positive correlation with Al2O3 (0.4 < r > 0.9) which is supportive of their residence in primary clay minerals such as kaolinite and illite-smectite. Additionally, a positive correlation of REEs with P2O5 (0.4 < r > 0.9) suggests their association with phosphate minerals (such as monazite, xenotime, apatite). Positive correlation with TiO2 (r > 0.7) corroborates the possible association of REEs with anatase. The morphology of the coal ash samples viewed in SEM showed the presence of Al2O3 and SiO2 enriched irregular-sponge particles likely derived from partly-fused clay minerals, which accounted for the lower extent of REE encapsulation. The Bhalukasba Surni coal block is potentially of economic importance due to its enrichment in Ge, Zr, and the REEs.