The development of a facile and efficient polymerization method to prepare polymers with unique nontraditional intrinsic luminescent (NTIL) properties is of vital importance and highly desired. In this work, a multicomponent tandem polymerization of alkyne and amines for the efficient preparation of NTIL poly(aminomaleimide)s (PAMIs) was established. Soluble and thermally stable PAMIs with acceptable molecular weights and well-defined structures are obtained in excellent yields after optimization. Sequence-controlled PAMIs with well-defined structures are obtained by using secondary amines for the amino-yne click reaction. The resulting amino-terminated PAMIs can be used as macromonomers for further polymerization. The PAMIs exhibit NTIL properties, and their emission in dimethyl sulfoxide/H2O mixtures can be tailored by changing the length of hydrophobic linker. Additionally, they exhibit low cytotoxicity and can be used as fluorescent bioprobes for bioimaging applications. Considering the mild polymerization conditions, readily available monomers, and excellent product performance, the present multicomponent tandem polymerizations opens up a new avenue to prepare functional polymeric materials with NTIL properties.