Constructing fibril morphology has been believed to be an effective method of achieving efficient exciton dissociation and charge transport in organic solar cells (OSCs). Despite emerging endeavors on the fibrillization of organic semiconductors via chemical structural design or physical manipulation, tuning of the fibril geometry, i.e., width and length, for tailored optoelectronic properties remains to be studied in depth. In this work, a series of alkoxythiophene additives featuring varied alkyl side chains connected to thiophene are designed to modulate the growth of fibril aggregates in cutting-edge polymer donors PM6 and D18. Molecular dynamics simulations and morphological characterizations reveal that these additives preferentially locate near and entangle with the side chains of polymer donors, which enhance the conjugated backbone stacking of polymer donors to form nanofibrils with the width expanding from 12.6 to 21.8 nm and the length increasing from 98.3 to 232.7 nm. This nanofibril structure is feasible to acquire efficient exciton dissociation and charge transport simultaneously. By integrating the fibril PM6 and L8-BO as the donor and acceptor layers in pseudo-bulk heterojunction (p-BHJ) OSCs via layer-by-layer deposition, an improvement of power conversion efficiency (PCE) from 18.7% to 19.8% is observed, contributed by enhanced light absorption, charge transport, and reduced charge recombination. The versatility of these additives is also verified in D18:L8-BO OSCs, with enhanced PCE from 19.3% to 20.1%, which is among the highest values reported for OSCs.