In this report, a sensitive and selective chemiluminescence (CL) biosensor for bovine serum albumin (BSA) coupled with a surface molecularly imprinted polymer nanocomplex using β-cyclodextrin/chitosan–magnetic graphene oxide as backbone material (β-CD/Cs–MGO–SMIP) was investigated. The material β-CD/Cs–MGO combined with β-cyclodextrin, chitosan and graphene oxide was used to provide multiple imprinting sites and a large surface area was characterized by SEM, XRD and FTIR. It was found that β-CD/Cs–MGO–SMIP followed the Langmuir isotherm equation and pseudo-second order sorption kinetics when binding the template. This material demonstrated fast mass transfer, a promoted rate of removal of the biomacromolecule and excellent recognition and adsorption ability for the imprinting cavities situated at the surface of β-CD/Cs–MGO, which enabled easy access to BSA. Subsequently, a highly sensitive CL biosensor for BSA was proposed based on the strong recognition effect between β-CD/Cs–MGO–SMIP and BSA which led to a high selectivity of the sensor, and the proposed biosensor could assay in the range 5.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mg mL⁻¹ with a detection limit of 1.1 × 10⁻⁷ mg mL⁻¹. The obtained recoveries were between 94% and 106% when determining samples.