By combining the theories of optimal control and coherent control, we derive an analytical formulation to evaluate the optimal 1-photon and n-photon fields together:with their relative phase and intensity in the optimal "1 + n"-coherent control scheme. The optimal coherent control exploits tailored light pulses to produce the best overlap with a predefined nuclear target in an electronically degenerate region. It also exploits explicitly the quantum interference between two optimal excitation pathways to achieve the product electronic selectivity. Numerical demonstrations are carried out to selectively control a minimum-uncertainty outgoing wave packet target in a molecular system. The electronically degenerate byproduct is shown to be completely discriminated against via the destructive interference between two optimal excitation pathways. The target considered in this paper would neither be achievable via the conventional continuous-wave coherent control nor via a single optimal control pathway in the weak response regime. proposed is also a time-dependent excitation frequency degeneracy condition that incorporates the evolution of carrier frequencies in the optimal coherent control with tailored light fields.