We presented a novel approach for pyrophosphate (PPi) sensing. Two tetraphenylethene (TPE)-functionalised pyridine salts (TPM and TPH) were designed and synthesized. Both of them exhibited weak emission in the solution state that originates from intramolecular charge transfer (ICT) from TPE to the pyridine; the addition of PPi into the TPM aqueous solution would enhance the fluorescence intensity, which eliminates the emission quenching effect of the iodide ion by the formation of PPi-sensor nanoparticles. The detection limit of TPM was determined to be as low as 133 nM. Meanwhile, a thin solid film of TPM that could detect PPi rapidly was conveniently prepared.