Supramolecular interactions and molecular conformations play significant role on producing fluorescent polymorphs with tunable emission in the solid state from single fluorophore. External stimuli-induced structural transformation from one polymorph to another polymorph without losing single crystalline character (single-crystal-to-single-crystal transition (SC-SC)) provides perfect model to understand the structure-property of molecules in the solid state and designing new functional fluorescent materials. Herein we have tailored the substituent groups in the aggregation-induced-emissive (AIE) tetraphenylethylene (TPE) based donor (D)-acceptor (A) fluorophores (TPPA-1-6) and explored fluorescent polymorphs formation and SC-SC transition in the solid state. TPPA-1 showed conformational fluorescent polymorphs via twisted and co-planar conformation between TPE phenyl group and cyanophenyl acceptor phenyl ring. However, single crystal analysis of other derivatives revealed that substituent groups and supramolecular interactions control the molecular conformation and SC-SC transition. Fluorophore with same substituent but positional change also show drastic effect on the fluorescent polymorphs formation and SC-SC transition. Substituents that can form strong intermolecular interactions stabilize the less stable co-planar structure whereas bulky substituents with weak intermolecular interactions produced twisted or both conformers. Photophysical, powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC) and thermogravimteric (TG) analysis were performed to substantiate and get insight on the structural transformation. The formation of fluorescent polymorphs and SC-SC transition exhibited tunable and switchable solid state fluorescence. The non-planar TPE core has been made use to demonstrate high contrast stimuli induced reversible fluorescence switching. Overall, the present studies attempted to gain information on the structural design for developing SC-SC transforming functional organic fluorescent materials that could be of potential interests for optoelectronic and display devices.