Herein, four planar cyclometalated platinum(II) complexes with a main ligand of enlarged aromatic rings have been assessed as effective anticancer theranostic agents for the first time. With an increased number of aromatic rings in the N∧N ligand, 1a-1d exhibit increased lipophilicity and cytotoxicity selectivity. The intensity of the Pt-Pt interaction of each complex can be indicated by an enhanced near-infrared (NIR) emission in phosphate-buffered saline (PBS), their binding activity with biomolecules of bovine serum albumin (BSA) is accompanied by a vivid turn-on green emission, and the intensity gradually decreased from 1a to 1d, which is consistent with the docking of two complexes with BSA. Both "turn-on" NIR and green emission of 1d can be mainly observed in nuclei of living cell within 24 h, while two phosphorescence traces of 1b were recorded in lysosomes by confocal imaging. Moreover, 1d shows the highest efficiency in inducing oncosis of Hela cells, and the relative process was investigated.