In this paper, we consider the existence and asymptotic behavior on mass of the positive solutions to the following system:under the mass constraintwhere a 1 , a 2 are prescribed, µ 1 , µ 2 , β > 0; α 1 , α 2 ∈ R, p ∈ (2, 4) and λ 1 , λ 2 ∈ R appear as Lagrange multipliers. Firstly, we establish a non-existence result for the repulsive interaction case, i.e., α i < 0(i = 1, 2). Then turning to the case of α i > 0(i = 1, 2), if 2 < p < 3, we show that the problem admits a ground state and an excited state, which are characterized respectively by a local minimizer and a mountain-pass critical point of the corresponding energy functional. Moreover, we give a precise asymptotic behavior of these two solutions as (a 1 , a 2 ) → (0, 0) and a 1 ∼ a 2 . This seems to be the first contribution regarding the multiplicity as well as the synchronized mass collapse behavior of the normalized solutions to Schrödinger systems with Sobolev critical exponent. When 3 ≤ p < 4, we prove an existence as well as non-existence (p = 3) results of the ground states, which are characterized by constrained mountain-pass critical points of the corresponding energy functional. Furthermore, precise asymptotic behaviors of the ground states are obtained when the masses of whose two components vanish and cluster to a upper bound (or infinity), respectively.