A novel totally chlorine-free bamboo-pulp bleaching process is provided. The invention relates to a novel totally chlorine free (TCF) bamboo-pulp bleaching process, is a new bionic bleaching technology for paper pulp. The invention essentially comprises the following procedures: (1) Synthesizing enzyme-imitated metal salen, using Schiff base salen to react with metallic organic acid salt to synthesize metal salen; (2) Pre-treatment bleaching bamboo pulp, carrying out bleaching pre-treatment on the oxygen delignification sulfate bamboo pulp with metal salen, NaOH, H2O2 and O2 existing; (3) Subsequent TCF bleaching, carrying out three bleaching treatments, namely, alkaline treating enhanced by hydrogen peroxide, bleaching by peroxy acid and bleaching by hydrogen peroxide the bamboo pulp pre-treated by enzyme-imitated metal salen. For the invention, the source is wide, the metal salen is easy to synthesize, the yield rate is high, the cost is low, the consumption is very low; the metal salen is easy to store, has no demanding requirement on the environment, can obviously improve the whiteness of paper pulp, reduce the load of waste water pollution in bleaching, and saves the use of bleaching chemicals.