In the present study, we have discovered and identified a new crystalline form of pinaverium bromide, pinaverium bromide dihydrate (C26H41BrNO4⋅Br⋅2H2O), whose single crystals can be obtained by recrystallization from a mixture of water and acetonitrile at room temperature. The obtained crystals were characterized by X-ray single-crystal diffraction, and their crystal structure was also solved based on X-ray single-crystal diffraction data. The results show that the final pinaverium bromide dihydrate model contains an asymmetric unit of one pinaverium bromide (C26H41Br2NO4) molecule and two water molecules that combine with the bromine ion through O–H⋯O and O–H⋯Br hydrogen bonds. Then, the adjacent pinaverium bromide dihydrates are linked by O–H⋯O, O–H⋯Br, and C–H⋯O hydrogen bonds. On the other hand, the experimentally obtained X-ray powder diffraction pattern is in good agreement with the simulated diffraction pattern from their single-crystal data, confirming the correctness of the crystal structure. Hirshfeld surface analysis was employed to understand and visualize the packing patterns, indicating that the H⋯H interaction is the main acting force in the crystal stacking of pinaverium bromide dihydrate.