We report a mechanistic study of the interactions in the sorption of volatile organic sulfur compound (VOSC) diethyl sulfide (DES) by zinc porphyrin aluminum MOF (actAl-MOF-TCPPZn) compound 3. First, interactions were studied under dynamic conditions with the vapor of DES in flowing air, using in situ time-dependent ATR-FTIR spectroscopy in a controlled atmosphere with a new facile spectroscopic mini-chamber. The first binding site includes μ(O-H) and COO- groups as detected by characteristic peak shifts. Control experiments with a model compound, which lacks porosity and these groups, show no peak shifts. An additional insight was obtained by DFT computations using small clusters. The kinetics of sorption of DES by compound 3 is of the Langmuir adsorption model and pseudo-first order with rate constant robs = 0.442 ± 0.056 min-1. Sorption of DES under static conditions in saturated vapor results in stoichiometric adsorption complex [Al-MOF-TCPPZn]1(DES)4 characterized by spectroscopic, structural and gravimetric methods; the adsorbed amount is very high (381 mg g-1 sorbent). The repetitive sorption and desorption of DES are conducted, with facile regeneration. Finally, the mechanistic details were determined by Raman and photoluminescence (PL) spectroscopy using a confocal Raman microscope. Photoexcitation of compound 3 at 405 nm into the Soret band of the metalloporphyrin linker shows the characteristic PL peaks of Q-bands: the purely electronic Q(0-0) and first vibronic Q(0-1) bands. Upon interaction with DES, preferential quenching of PL from the Q(0-0) band occurs with a significant increase of the signal of the vibronic Q(0-1) band, reflecting bonding to the metalloporphyrin ring. Compound 3 is of interest to mechanistic studies of VOSCs, their removal from air, and optical chemo-sensing.