The interest in green processes and products has increased, in order to reduce the negative impact of many industrial processes on the environment. Solvents, which play a crucial role in the fabrication of membranes, need to be replaced by sustainable and less toxic solvent alternatives for commonly used polymers. The purpose of this study is the fabrication of greener hollow fiber membranes based on polyacrylonitrile (PAN), substituting dimethylformamide (DMF) by less toxic mixtures of ionic liquids (IL) and dimethylsulfoxide (DMSO). A thermodynamic analysis was conducted, estimating the Gibbs free energy of mixing to find the most convenient solution compositions. Hollow fiber membranes were manufactured and optimized. As a result, a uniform pattern and high porosity were observed in the inner surface of the membranes prepared from the ionic liquid solutions. The membranes were coated with a polyamide layer by interfacial polymerization. The hollow fiber membranes were applied in forward osmosis experiments by using sucrose solutions as draw solution.