In the present work, the effect of α-Fe
2
O
3
-nanoparticles (IONPs) supplementation at varying doses (0, 10, 20 and, 30 mg L
−1
) at the intermittent stage (after 12th day of growth period) was studied on the growth and biogas production potential of
Chlorella pyrenoidosa
. Significant enhancements in microalgae growth were observed with all the tested IONPs doses, the highest (2.94 ± 0.01 g L
−1
) being at 20 mg L
−1
. Consequently, the composition of the biomass was also improved. Based on the precedent determinations, theoretical chemical oxygen demand (COD
th
) as well as theoretical and stoichiometric methane potential (TMP, and SMP) were also estimated. The COD
th
, TMP, SMP values indicated IONPs efficacy for improving biogas productivity. Further, the biochemical methane potential (BMP) test was done for IONPs supplemented biomass. The BMP test revealed up to a 25.14% rise in biogas yield (605 mL g
–1
VS
fed
) with 22.4% enhanced methane content for 30 mg L
−1
IONPs supplemented biomass over control. Overall, at 30 mg L
−1
IONPs supplementation, the cumulative enhancements in biomass, biogas, and methane content proffered a net rise of 98.63% in biomethane potential (≈ 2.86 × 10
4
m
3
ha
−1
year
−1
) compared to control. These findings reveal the potential of IONPs in improving microalgal biogas production.