Porphyrin-cored bile acid dendrimers containing deoxymethyl cholate and methyl cholate units at the periphery, have been synthesized by convergent methodology using a click chemistry approach and characterized by ¹H and ¹³C NMR and MALDI-TOF MS data. The absorption–emission behavior of dendrimers and its modulation under the influence of the dendritic environment is also investigated. The therapeutic efficacy of the bile acid dendrimers for the inhibition of the growth of tumor cells (MIA PaCa-2) increases as the dendrimer generation increases.