The blue algae can be used as a nitrogen agent for promoting biological coalbed methane, but its applicability and microbial mechanism in different microbial enhanced coalbed methane technologies kept unknown. This study evaluated the methanogenic efficiency of blue algae addition with a mass ratio of 10% under fermentative degradation and microbial electrolytic cell technologies, and studied the changes of coal microstructure, surface functional groups, organic components and microbiome. The results showed that the algae addition affected the micro-concave-convex structure, non-uniform distribution of micro-particles and micro-cracks of coals, and finally increased the methanogenic rate by 1.74–2.66 times. The algae addition mainly affected the coal organic components including hydroxyl structure, hydrocarbon structure, aliphatic oxygen-containing functional groups and aromatic structure, as well increased the humus acids and microbial metabolites in fermentation broth; among them, the increased metabolites showed great differences between different technologies. The algae addition mainly increased the genera belonging to phylum Bacillota (such as Bacillus and Clostridium) and methanogens (Methanosarcina and Methanoculleus). These Bacillota groups could degrade organic matter into acetate and methanol via pathways of glycolysis and benzoate degradation, which provided substrates for such methanogens. This study strengthened the effectiveness of blue algae in enhancing technologies for biological coalbed methane.