A novel fluorescent organogelator NSS comprised of CN and NNH units was designed and characterized. By light irradiation, NSS could undergo trans to cis transformation both in solution and gel state, which was accompanied by dramatic color, fluorescence intensity, and emission color changes, indicating the photochromic property of NSS. Both of the gels in E-isomeric and Z-isomeric forms could selectively response to fluoride anion among tested anions. Further study presented that the two isomers displayed different signal outputs and binding mechanisms toward fluoride anion. Especially, the organogel of NSS in the E-isomeric form showed selective, visual, and reversible sensing for fluoride anion. Beside the above functions, the organogel could also response to ultrasound and heating stimuli, thus endowing the organogel with multi-stimuli responsive properties.