Three-primary-color luminescent materials are highly desirable to construct white-light emitting resource,multi-color optical displays,and tunable photonic applications.However,the efficient strategy to establish the three-primary-color systems with unique photofunctionalities is still rather limited,particularly for molecular materials.Herein,we developed a molecular cocrystal route to obtain three-primary-color emissive materials by tuning different donor-acceptor units based on the same chromophore(4,4\'-bis(2,5-dimethylstyryl)biphenyl,Bdb).The warm and cold white-light together with multi-color emission in most of visible region can be highly adjusted by rationally tuning different mixture components of three-primary-color cocrystals through an energy transfer mechanism.Furthermore,the blue/green/red emitters endow Bdb molecular cocrystals novel color-tunable photonic properties(such as one-dimensional(1D)/2D optical waveguide,polarized fluorescence,up-conversion lu-minescence,and amplified spontaneous emission),benefitting from their well-defined micro/nanostructures and high crystal-linity.Particularly,the high luminescence quantum yield(82.49％)and polarized anisotropy(0.723)outperform most of state-of-the-art molecular crystalline materials.Therefore,this work supplies an effective way to fabricate new types of three-primary-color phosphors through luminescent cocrystals,which have promising applications in the fields of full-color displays,white-light irradiation,low-dimensional optical polarization,and micro/nanophotonics.