In this work,we designed and synthesized a novel naphthalenediimide-based n-type conjugated polymer PNDICI,which bears asymmetric backbone containing a 3-chlorothiophene unit.The asymmetric structure associated with steric effects of the chlorine atom imparts remarkable solubility to PNDICI in various organic solvents,enabling the fabrication of all-polymer solar cells (all-PSCs) by using an environmentally friendly solvent of d-limonene.Combined with a novel pyrrolo[3,4-f]benzotriazole-5,7(6H)-dione based p-type conjugated polymer P2F-Si with deep highest occupied molecular orbital energy level,the resulting d-limonene-processed all-PSCs presents an impressively high open-circuit voltage of approaching 1.0 V,corresponding to a very small energy loss of 0.49 eV.Through further morphology optimization by using γ-valerolactone,we demonstrated an impressive device efficiency of 4.2％,which is among the best photovoltaic performance of devices processed using d-limonene and comparable to that processed by conventional solvent,suggesting the great promise of using greener solvent for fabricating high-performance all-PSCs.