Sensitizing crystalline silicon (c-Si) with an infrared-sensitive material, such as lead sulfide (PbS) colloidal quantum dots (CQDs), provides a straightforward strategy for enhancing the infrared-light sensitivity of a Si-based photodetector. However, it remains challenging to construct a high-efficiency photodetector based upon a Si:CQD heterojunction. Herein, we demonstrate that Si surface passivation is crucial for building a high-performance Si:CQD heterojunction photodetector. We have studied one-step methyl iodine (CH3I) and two-step chlorination/methylation processes for Si surface passivation. Transient photocurrent (TPC) and transient photovoltage (TPV) decay measurements reveal that the two-step passivated Si:CQD interface exhibits fewer trap states and decreased recombination rates. These passivated substrates were incorporated into prototype Si:CQD infrared photodiodes, and the best performance photodiode based upon the two-step passivation shows an external quantum efficiency (EQE) of 31% at 1280 nm, which represents a near 2-fold increase over the standard device based upon the one-step CH3I passivated Si.