Pullulans from various sources were dissolved with and without additives to be spun. The additives employed were glycerol, maltitol and chitosan. The introduction of glycerol and chitosan respectively gave the effects of softening and strengthening of the fibers. The chitosan improved a fiber orientation which might resulted from hydrogen bonding or bonding interruption by chitosan molecules with the pullulan polymers. When urea was added in the pullulan solution as a hydrogen bond interrupter, the viscosity was reduced, which indicated a reduction of the intensity of hydrogen bonding. The pullulan exhibiting lower viscosity reduction by incorporating the urea addition showed better spinnability than that exhibiting higher viscosity drop. The better spinnability would obtain from less agglomerated solution introduced by hydrogen bonding.