Abstract: Controlling environmental humidity level and thus moisture interaction with an electrospinning solution jet has led to a fascinating range of polymer fibre morphological features; these include surface wrinkles, creases and surface/internal porosity at the individual fibre level. Here, by cross-correlating literature data of far-field electrospinning (FFES), together with our experimental data from near-field electrospinning (NFES), we propose a theoretical model, which can account, phenomenologically, for the onset of fibre microstructures formation from electrospinning solutions made of a hydrophobic polymer dissolved in a water-miscible or polar solvent. This empirical model provides a quantitative evaluation on how the evaporating solvent vapour could prevent or disrupt water vapor condensation onto the electrospinning jet; thus, on the condition where vapor condensation does occur, morphological features will form on the surface, or bulk of the fibre. A wide range of polymer systems, including polystyrene, poly(methyl methacrylate), poly-l-lactic acid, polycaprolactone were tested and validated. Our analysis points to the different operation regimes associated FFES versus NFES, when it comes to the system’s sensitivity towards environmental moisture. Our proposed model may further be used to guide the process in creating desirable fibre microstructure.