The invention relates to a manufacturing method of a high-efficiency silicon substrate photovoltaic cell. The manufacturing method comprises the following steps: forming a suede layer on the upper surface of an N-type monocrystalline silicon piece; forming a P-type silicon layer on the upper surface of the N-type monocrystalline silicon piece; depositing a silicon nitride passivation layer on theP-type silicon layer, and carrying out etching treatment on the silicon nitride passivation layer so as to form an opening in an area in which an upper electrode is to be formed and expose the P-typesilicon layer; spin-coating a solution containing cobaltous sulfide nanopowder on the upper surface of the N-type monocrystalline silicon piece, carrying out first annealing treatment, then spin-coating a solution containing zirconium ethoxide, carrying out second annealing treatment; spin-coating a solution containing bis(pentane-2,4-dionato-O,O')bis(propan-2-olato)titanium on the lower surface of the N-type monocrystalline silicon piece, carrying out annealing treatment, then spin-coating a solution containing black phosphorus alkene, and carrying out drying treatment; forming the upper electrode on the upper surface of the N-type monocrystalline silicon piece, and forming a lower electrode on the lower surface of the N-type monocrystalline silicon piece.