Lanthanide-based coordination polymers (CPs) have received great attention due to their tuneable structures and excellent luminescence properties. However, limited by the stability and micro/nanoscale morphology, a very small number of lanthanide-based CPs have been used for photonic applications. Herein, we present the synthesis of Eu-based CPs (compound 2) with highly regular one-dimensional (1D) microrod morphology by in situ structure transformation from compound 1. Moreover, the Eu-based CP microrods have an excellent stability and a high photoluminescence quantum yield (PLQY), and the distance-dependent PL spectra also exhibited typical characteristics of photoactive waveguides with a low optical-loss coefficient (0.00894 dB μm-1) during propagation. These intriguing behaviors not only extend the research field of optical waveguides through lanthanide-based CPs, but also provide an opportunity for further application in optical communication systems.