A high-silicon steel sheet is excellent in terms of punching workability and magnetic property. The high-silicon steel sheet has a chemical composition containing, by mass %, C: 0.02% or less, P: 0.02% or less, Si: 4.5% or more and 7.0% or less, Mn: 0.01% or more and 1.0% or less, Al: 1.0% or less, O: 0.01% or less, N: 0.01% or less, and the balance being Fe and inevitable impurities, a grain-boundary oxygen concentration (oxygen concentration with respect to chemical elements segregated at grain boundaries) of 30 at % or less, and a microstructure in which a degree of integration P(211) of a {211}-plane of α-Fe on a surface of the steel sheet is 15% or more P(211)=p(211)/S×100(%), wherein S=p(110)/100+p(200)/14.93+p(211)/25.88+p(310)/7.68+p(222)/1.59+p(321)/6.27+p(411)/1.55, and p(hkl): integrated intensity of a peak of X-ray diffraction of an {hkl}-plane.