Uniform and beads free fibers of pristine syndiotactic PMMA (s-PMMA), isotactic PMMA (i-PMMA), and their blends in the ratio of s:i = 3:1, 1:1 and 1:3 were successfully prepared using the electrospinning technique. The tactic PMMA blend fibers showed unique thermal stability and glass transition temperatures compared to their pristine counterparts. An interesting endotherm peak was observed for the s:i = 1:3 electrospun fibers, which might indicate a complex formation between the two tactic PMMAs. Systematic surface functionalities study by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) revealed the interactions between these two tactic PMMAs. Biocompatibility of tactic PMMA and their blend fibers was first time comparably investigated using HeLa as the model mammalian cell line; an intriguing observance was first revealed that the blend fibers showed better biocompatibility than both pristine ones, though the behind mechanism is not well understood yet. (C) 2014 Elsevier Ltd. All rights reserved.