In this study, the bending performance of a separable cross-laminated timber (CLT)–concrete composite slab for reducing environmental impact was investigated. The slab has consisted of CLT and eco–concrete, and round-notch shape shear connectors resist the shear force between the CLT and eco-concrete. The eco–concrete was composed of a high-sulfated calcium silicate (HSCS) cement, which ensures low energy consumption in the production process. The bending stiffness and load-carrying capacities of the slab were theoretically predicted based on the shear properties of the notch connectors and validated with an experimental test. The shear properties of two types of notch shear connectors (Ø100 mm and Ø200 mm) were measured by planar shear tests. As a result, the stochastically predicted bending stiffness of the slab (with Ø100 mm shear connector) was 0.364 × 1012 N mm2, which was almost similar to test data. The load-carrying capacities of the slab were governed by the shear failure of the notch connectors, and the lower fifth percentile point estimate (5% PE) was 21.9 kN, which was 7.9% higher than the prediction (20.2 kN). In a parameter study, the effect of notch diameter for the CLT-concrete slab span was analyzed depending on the applied loads, and the maximum spans of the slab with Ø100 mm notch or Ø200 mm notch were not significantly different.