A 3-silolene derivative, 2,2,5,5-tetrakis(dimethylsilyl)-1,1-dimethyl-3,4-diphenyl-3-silolene (TDMSHS), is first synthesized and characterized by X-ray diffraction crystallography and spectroscopic methods. Hydrosilylation polymerization of TDMSHS with 1,1-dimethyl-2,5-bis(4-ethynylphenyl)-3,4-diphenylsilole in the presence of Karstedt's catalyst generates a stereoregular silole-containing hyperbranched poly(silylenevinylene) (hb-SPSV) with a high molecular weight ($\overline{M}_{\rm w}$ = 146 000, $\overline{M}_{\rm w}$/$\overline{M}_{\rm n}$ = 1.5) in high yield (approximate to 95%). hb-SPSV exhibits excellent thermal stability and strong fluorescence, and the emission of its aggregates in aqueous mixture can be quenched efficiently by picric acid with large quenching constants KSV up to 414400 M-1.