Hollow fiber membranes of polyvinylidene fluoride (PVDF) were prepared by incorporating varying concentrations of hydrophilic surface-modifying macromolecules (LSMM) and a constant amount of polyethylene glycol (PEG) additives. The membranes were fabricated by the dry-wet spinning technique. The prepared hollow fiber membranes were dip-coated by hydrophobic surface-modifying macromolecules (BSMM) as the final step fabrication. The additives combination is aimed to produce hollow fiber membranes with high flux permeation and high salt rejection in the matter of seawater desalination application. This study prepares hollow fiber membranes from the formulation of 18 wt. % of PVDF mixed with 5 wt. % of PEG and 3, 4, and 5 wt. % of LSMM. The membranes are then dip-coated with 1 wt. % of BSMM. The effect of LSMM loading on hydrophobicity, morphology, average pore size, surface porosity, and membrane performance is investigated. Coating modification on LSMM membranes showed an increase in contact angle up to 57% of pure, unmodified PVDF/PEG membranes, which made the fabricated membranes at least passable when hydrophobicity was considered as one main characteristic. Furthermore, The PVDF/PEG/4LSMM-BSMM membrane exhibits 161 °C of melting point as characterized by the DSC. This value indicates an improvement of thermal behavior shows so as the fabricated membranes are desirable for membrane distillation operation conditions range. Based on the results, it can be concluded that PVDF/PEG membranes with the use of LSMM and BSMM combination could enhance the permeate flux up to 81.32 kg·m−2·h−1 at the maximum, with stable salt rejection around 99.9%, and these are found to be potential for seawater desalination application.