Ordered luminescent ultrathin films (UTFs) have been fabricated by means of layer‐by‐layer assembling of Na9[EuW10O36]·32H2O (abbreviated as EuW10), the photoactive organic molecule of bis(N‐methylacridinium) nitrate (denoted BNMA), and exfoliated Mg2Al‐LDH (layered double hydroxide). The assembly process has been monitored by UV/Vis absorption and fluorescence spectroscopy to obtain a stepwise and regular growth of the UTFs upon increasing the deposited cycles. The alternative intercalation of EuW10 and BNMA into LDHs results in the formation of well‐ordered UTFs with tunable color. Each LDH monolayer with rigid structure provides a confined and protective microenvironment for BNMA and EuW10, and the guest molecules exhibit orientation effect.