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Abstract Nanoscopic packing structures crucially determine the charge conduction and the consequent functionalities of organic semiconductors including bulk heterojunctions (BHJs), which are dependent on various processing parameters. Today's high‐performance colloidal quantum dot photovoltaics (CQDPVs) employ functional organic semiconductors as a hole transport layer (HTL). However, the processing of those films replicates a protocol dedicated to high‐performance organic PVs, and thus little is known about how to control the molecular packing structures to maximize the hole extraction function of the HTLs. Herein, it is uncovered that the random‐oriented, but closer‐packed BHJ crystallites, constructed by 1,2‐dichlorobenzene (o‐DCB) as a solvent, allow exceptional charge conduction vertically across the film and restrict diffusion‐driven charge transfer process, enabling ultrafast hole funneling from CQD to BHJ to be extracted. As a result, a power conversion efficiency of 13.66% with high photocurrent >34 mA cm⁻²is achieved by employingo‐DCB‐processed BHJ HTL, far exceeding the performance of the CQDPV solely employing neat polymer HTL. A charge conduction mechanism associated with the BHJ HTL structure suppressing the bimolecular recombination is proposed. This works not only suggests key principles to control the packing structures of organic HTLs but also opens a new avenue to boost optoelectronic performance.