In this investigation, MIL-101-NH2 chemically functionalized with cobalt(II) tetrasulfophthalocyanine (CoTSPc) through a superior electrostatic interaction reaction. The configuration of the synthesized composite was characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermal gravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscope (SEM), and inductively coupled plasma optical emission spectrometer (ICP-OES). This spongy composite showed excellent catalytic activity in the aerobic oxidation reaction of primary and secondary benzylic alcohols. The generated catalyst's behavior was examined to synthesize propargylamines via tandem oxidative A3 coupling process to illustrate the maximum potential of the synthesized catalyst. Utilizing air as an oxidant, operational simplicity, easy preparation, apt yielding, non‐hazardous nature of the catalyst, and reusability are the essential advantages of this catalyst.