Pyrite nanocrystals are currently considered as a promising material for large scale photovoltaic applications due to their non‐toxicity and large abundance. While scalable synthetic routes for phase‐pure and shape controlled colloidal pyrite nanocrystals have been reported, their use in solar cells has been hampered by the detrimental effects of their surface defects. Here, we report a systematic study of optical and electronic properties of pyrite nanocrystal thin films employing a series of different ligands varying both the anchor and bridging group. The effect of the ligands on the optical and electronic properties is investigated by UV‐vis/NIR absorption spectroscopy, current voltage characteristic measurements and surface photovoltage spectroscopy. We find that the optical absorption is mainly determined by the anchor group. The absorption onset in the thin films shifts up to ∼100 meV to the red. This is attributed to changes in the dielectric environment induced by different anchors. The conductivity and photoconductivity, on the other hand, are determined by combined effects of anchor and bridging group, which modify the effective hopping barrier. Employing different ligands, the differential conductance varies over four orders of magnitude. The largest redshift and differential conductance are observed for ammonium sulfides and thiolated aromatic linkers. Pyridine and long chain amines, on the other hand, lead to smaller modifications. Our findings highlight the importance of surface functionalization and interparticle electronic coupling in the use of pyrite nanocrystals for photovoltaic devices.