Nb/Yb co-doped RbTiOPO₄ (RTP) crystals were successfully grown by a top-seeded solution growth method from two different kinds of flux systems. 5%Nb/3%Yb: RTP crystal with more transparency was obtained from the mixed solvent containing MoO₃. The chemical composition was analyzed by Electron Probe Microanalyzer (EPMA), and the result indicated that co-doping of Nb and Yb into RTP can greatly increase the concentration of Yb in RTP crystal. The addition of MoO₃ into self-flux system can improve the quality of as-grown crystals, but it is not helpful to introduce Yb into crystal. The electronic structures of Nb/Yb: RTP crystals were analyzed using X-ray photoelectron spectra (XPS). The results show that the binding energy difference between O 1s and P 2p levels (ΔBE (O-P)) increases firstly with the increase of Yb content, and then decreases with Nb content increasing, which is associated with the covalency change of O-P bonds in crystals. However, the doping has little influence on the chemical bond properties of O-Ti. The FL spectra of Nb/Yb: RbTiOPO₄ crystals were also analyzed, and five emission peaks characteristic of Yb^3t ions were observed.