Four compounds 4‐[3,6‐di(carbazol‐9‐yl)carbazol‐9‐yl]isoquinoline (TCIQ), 3‐[3,6‐di(carbazol‐9‐yl)carbazol‐9‐yl]pyridine (TCPy), 4‐(carbazol‐9‐yl)isoquinoline (4CIQ), and 3‐(carbazol‐9‐yl)pyridine (CPy) containing pyridyl or isoquinolyl were designed and synthesized to co‐deposition with copper iodide (CuI) to form luminescent Cu(I) complex doped film in situ, which could be utilized as the emissive layer in organic light‐emitting diodes (OLEDs). It is found that simple tri‐layered yellow and white OLEDs can be achieved by co‐depositing CuI and TCIQ with tuning ratios. The compound TCIQ serves a dual role as both a ligand for forming the emissive Cu(I) complex and as a host matrix for the formed emitter in yellow OLEDs, and a third role as a blue emitter in white OLEDs.