A turn-on fluorescence sensing system for mercuric (Hg2+) ions relying on a modified rhodamine B-chitosan fluorophore moiety was developed. This novel sensing approach relies on the simultaneous electrospinning of chitosan and rhodamine B hydrazide with phenylisothiocyanate functionality in hexafluoroisopropanol solution at 3.4 kV cm(-1). The electrospun mats exhibited not only considerably enhanced fluorescence intensity in the presence of mercury ions, a result attributed to the ring opening of the spirolactam unit of the rhodamine-based fluorophore, but also a remarkably high sensitivity and selectivity toward Hg2+. In effect, the strategy has the potential to open new avenues in the design and development of other high-performance nanofibrous sensing materials for detecting target metal species of environmental interest.