We present the defect analysis by photoluminescence (PL) spectroscopy of CdSexTe1-x thin films, grown with varying Se content by a co-sputtered deposition method. We observe a peak at 1.203 eV in the CdSexTe1-x film for x = 0.21, which shifts towards higher energies with increase in laser power. This peak was assigned to a donor-to-acceptor (DAP) transition, with a measured j-shift of ∼4.7 meV/decade. Temperature dependent PL intensity measurements confirm that the observed DAP peak involves a shallow defect state of binding energy ∼34.7 meV. In contrast, a free-to-bound (FB) peak at 1.294 eV involving a shallow defect of binding energy ∼18.3 meV was observed in the CdSexTe1-x film for x = 0.14. Additionally, we observe band edge emission at 1.452 eV and 1.448 eV in CdSexTe1-x films for x = 0.14 and x = 0.21 respectively. Our analysis shows that the Se concentration not only changes the band gap energy of the resulting CdSexTe1-x alloy thin film, but also modifies the nature of the dominant observed defect emission.