Ratiometric detection of analyte is highly deserving since the technique is free from background correction. This work reports the design and synthesis of a pyridine-end oligo p-phenylenevinylene (OPV) derivative, 1 and its application in ratiometric dual-mode (both colorimetric and fluorogenic) recognition of dual anions, bisulphate (LOD= 12.5 ppb) followed by fluoride (LOD= 18.2 ppb) by sequence-specific relay (SPR) technique. The colorless probe turns brown with addition of bisulphate and again becomes colorless with the sequential addition of fluoride ion. In addition to such naked-eye color change, interestingly the ratiometric spectroscopic signals are reversible and evidently, the probe is reusable for several cycles. Besides, in presence of bisulphate, the protonated probe molecules, owing to their larger amphiphilic characteristics, formed self-assembled nanostructures. In addition to colorimetric and fluorescent changes, 1H NMR titration and systematic DFT study evidently establish the underneath proton transfer mechanisms. Such reusable OPV-based chemosensor particularly with the capability of naked-eye recognition of dual anions using the SPR technique is seminal and possibly the first report in the literature.