The structure of the canted antiferromagnet β‐p‐NCC6F4CNSSN (1) was determined from synchrotron powder‐diffraction studies in the pressure range 0–21.6 kbar. Radical 1 crystallizes in the orthorhombic space group Fdd2, but undergoes an asymmetric contraction of the unit‐cell size with increasing pressure. At the molecular level, this contraction of the unit cell is simultaneously accommodated by: 1) an increase in twist angle between aryl and heterocyclic rings; and 2) a shortening of the intermolecular S⋅⋅⋅N contacts, which propagate the magnetic‐exchange pathway. DFT calculations based on the structures in this pressure range revealed an increase in the magnetic‐exchange interaction (J) with increasing pressure, and an excellent correlation was observed between J and the magnetic‐ordering temperature, which increased from 36 K at ambient pressure up to 70 K at 16 kbar. Squeeze me! The organic magnet p‐NCC6F4CNSSN revealed a dramatic increase in the magnetic‐ordering temperature under pressure reaching 70 K at 16 kbar. Structure determination from powder X‐ray diffraction (PXRD) data coupled with DFT calculations revealed that this is associated with a shortening of the intermolecular S⋅⋅⋅N contacts (see figure).