Antimony　sulfide　(Sb2S3)　is　emerging　as　a　popular　photovoltaic　candidate　for　thin-film　solar　cells　due　to　its　large　absorption　coefficient,　suitable　bandgap,　nontoxic,　and　earth-abundant　nature.　The　performance　of　thermally　evaporated　Sb2S3　devices　is　severely　restricted　by　interfacial　recombination　leading　to　high　open-circuit　voltage　(V-OC)　losses.　CdS　as　electron　transport　layer　(ETL)　has　overcome　this　problem,　but　triggered　lower　J(SC)　issues　due　to　parasitic　absorption　loss　conceding　to　its　smaller　bandgap.　Herein,　a　spray　pyrolysis　method　is　adopted　for　the　deposition　of　a　uniform　and　compact　Zn-doped　TiO2　film　with　tuned　energy　levels　to　facilitate　charge　extraction　and　transport.　The　solar　cell　fabricated　with　a　modified　TiO2　ETL　holds　superior　interface　quality,　high　build-in　potential,　and　suppressed　recombination　losses,　therefore　pronouncedly　improves　theV(OC).　As　a　result,　the　efficiency　of　the　device　is　boosted　from　4.41%　to　5.16%,　a　recordV(OC)　of　702　mV　for　Cd-free　full-inorganic　Sb(2)S(3)solar　cell　is　achieved.　These　findings　are　expected　to　be　implemented　in　other　Sb-chalcogenide　solar　cells　to　further　enhance　the　device　performance.