Allylamine-functionalized silicon quantum dots (ASQDs) of high photostability are synthesized by a robust inverse micelle method to use the material as a fluorescent probe for selective recognition of thiocyanate (a biomarker of a smoker and a nonsmoker). The synthesized ASQDs were characterized by absorption, emission, and Fourier transform infrared spectroscopy. Surface morphology is studied by transmission electron microscopy and dynamic light scattering. The synthesized material exhibits desirable fluorescence behavior with a high quantum yield. A selective and accurate (up to 10-10 M) method of sensing of thiocyanate anion is developed based on fluorescence amplification and quenching of ASQDs. The sensing mechanism is investigated and interpreted with a crystal clear mechanistic approach through the modified Stern-Volmer plot. The developed material and the method is applied to recognize the anion in the human blood sample for identification of the degree of smoking. The material deserves high potentiality in the field of bio-medical science.