Molecular ordering within the photoactive layer plays a crucial role in determining the device perfor-mance of organic solar cells(OSCs).However,the simultaneous molecular ordering processes of polymer donors and non-fullerene acceptors(NFAs)during solution casting usually bring confinement effect,lead-ing to insufficient structural order of photovoltaic components.Herein,the molecular packing of m-INPOIC NFA is effectively formed through a heating induced aggregation strategy,with the aggregation of PBDB-T,which has a strong temperature dependence,is retarded by casting on a preheated substrate to reduce its interference toward m-INPOIC.A sequent thermal annealing treatment is then applied to promote the ordering of PBDB-T and achieve balanced aggregation of both donors and acceptors,result-ing in the achievement of a maximum efficiency of 13.9％of PBDB-T:m-INPOIC binary OSCs.This work disentangles the interactions of donor polymer and NFA during the solution casting process and develops a rational strategy to enhance the molecular packing of NFAs to boost device performance.