In the present paper, we consider the coupled Schrödinger systems with critical exponent:Here, Ω ⊂ R 3 is a smooth bounded domain, d ≥ 2, β ii > 0 for every i, and, where λ 1 (Ω) is the first eigenvalue of −∆ with Dirichlet boundary conditions and λ * (Ω) ∈ (0, λ 1 (Ω)). We acquire the existence of least energy positive solutions to this system for weakly cooperative case (β ij > 0 small) and for purely competitive case (β ij ≤ 0) by variational arguments. The proof is performed by mathematical induction on the number of equations, and requires more refined energy estimates for this system. Besides, we present a new nonexistence result, revealing some different phenomena comparing with the higher-dimensional case N ≥ 5. It seems that this is the first paper to give a rather complete picture for the existence of least energy positive solutions to critical Schrödinger system in dimension three.