Raw algal lipids (RALs) and their derivatives (fatty acid methyl esters; FAMEs) were investigated as biocollectors for the recovery of coal from ash-rich fine coal waste by froth flotation. Testing was done on fine coal discards from two South African sites—a high ash (50%), high sulphur (5.7%) sample and a lower ash (26%), low sulphur (0.91%) sample. The yield and recovery of combustibles on using biocollectors was similar to, or better than, with oleic acid, a polar collector demonstrated as a good collector in previous research. The RALs and FAMEs reduced the ash and sulphur content of the combustible fraction of the high ash-high sulphur sample to between 23–28% and 1.9–3.3%, respectively. The chemical modification of RALs to FAMEs provided potential for improving the selectivity of the recovery of combustibles. It also resulted in a change of the optimum operating pH, with RALs yielding better results at the natural pH of the sample (pH 2.7), while FAMEs performed best at pH 7.