A second polymorph of an anhydrous 1:1 caffeine citric acid cocrystal (C 8 H 10 N 4 O 2 , C 6 H 8 O 7 ) is reported. Crystals were analyzed using single crystal X-ray diffraction and the structure was solved in the monoclinic space group P2 1 /c with unit cell parameters a = 13.7783(8) Å , b = 12.3149(8) Å , c = 9.6587(6) Å , and b = 92.854(4)°. The three dimensional hydrogen bonding network is compared to the two dimensional network of the previously reported polymorph. Graphical Abstract A second polymorph of an anhydrous 1:1 caffeine citric acid cocrystal (C 8 H 10 N 4 O 2 , C 6 H 8 O 7 ) is reported, and the three dimensional hydrogen bonding network is compared to the two dimensional network of the previously reported polymorph.