A specific organization of optically active nanoscale objects can greatly affect the optical response of a system. Here, we report the controlled modification of the fluorescent emission by the assembly of water-soluble quantum rods (QRs). Our study combines optical, electron microcopy, and X-ray scattering characterizations to reveal a correlation between the self-assembly behavior of QRs into ordered 3D-arrays and the optical properties (luminescence) of formed assemblies, where the observed optical response is highly dependent on the QR aspect ratio. Specifically, shorter, 18 nm long QRs (QR18), exhibiting a well-defined smectic packing, demonstrate an enhancement of the emission intensity accompanied by a red shift and a lifetime reduction. In contrast, 40 nm long QRs (QR40), forming a columnar phase, does not show these optical properties.