A combinatorial in situ three-component chiral oxazoline-Schiff base copper(II) complex catalyst formation method was developed. This simple combinatorial chiral catalyst approach provided a modular library of chiral oxazoline-Schiff base copper(II) complex catalysts. The catalytic activity of these in situ generated catalysts can be rapidly and conveniently evaluated in the asymmetric Henry reaction. Moderate to good yields and enantioselectivities (up to 92% ee) were obtained under the optimized condition. The combination of modular three-component catalyst formation and in situ asymmetric reaction provides a new technology in asymmetric catalysis.