Water-dispersible, single-crystalline, and fluorescent colloidal crystals with curved edges were fabricated from π-conjugated chromophores 2,5-bis(α-cyano-4-bromostyryl)thiophene (CN-BST) and 2,5-bis(α-cyanostyryl)thiophene (CN-ST) via reprecipitation. The colloidal crystal growth occurred in a nonclassical pathway through alignment of seed particles. The effects of torsion and planarity were examined through DFT calculations and photoluminescence spectroscopy. The bromine end groups were shown not to have a significant role in bringing absorption or fluorescent spectral changes, however, had endowed the molecules to interact in an angular geometry, conferring additional stability and rigidity to the CN-BST colloidal crystals. Most importantly, secondary Br-Br interactions in the solid state shielded and stabilized the associative dimeric interactions of the type, (i) face-to-face π-stack, (ii) slip-stack, (iii) C-H···N, and (iv) C-H···π with different strengths. Both classes of colloidal crystals exhibited rectifying diodic behavior with a higher threshold voltage of 3.0 V for CN-BST versus 2.4 V for CN-ST. The characteristic transport is attributed to the compact molecular stacking in the crystalline state, along with the electron-withdrawing nature of the CN functionality integrated into the thiophenic molecular structure. © 2016 American Chemical Society.