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The intensity ratio of Fe XIV 264.765A/274.203A is useful to determine the electron density of solar corona, and the relationship between the electron density and the intensity ratio obtained from a model should be evaluated using laboratory plasmas to estimate the electron density more precisely. We constructed a new collisional–radiative model (CR-model) for Fe XIV (an Al-like iron ion) by considering the processes of proton-impact excitation and electron-impact ionization to the excited states of a Mg-like iron ion. The atomic data used in the CR-model were calculated using the HULLAC atomic code. The model was evaluated based on laboratory experiments using a compact electron beam ion trap, called CoBIT, and the Large Helical Device (LHD). The measured Fe XIV 264.785 Å/274.203 Å line intensity ratio with CoBIT was 1.869 ± 0.036, and it agreed well with our CR-model results. Concurrently, the measured ratio using LHD was larger than the results of our CR-model and CHIANTI. The estimated electron densities using our CR-model agreed with those from CHIANTI within a factor of 1.6–2.4 in the range of ne≈1010−11cm−3. Further model development is needed to explain the ratio in a high-electron density region.