Strong photovoltaic effects on photoluminescence (PL) spectra in InGaN/GaN blue light emitting diodes were investigated. Due to severe carrier escape from quantum wells, significant photovoltaic effects occur in PL measurement in open-circuit condition, which strongly affect the PL peak position and intensity. We reveal that proper correlation between electroluminescence and PL peak positions cannot be obtained without proper consideration of the photovoltaic effects. By changing sample temperature and the PL excitation power, the generated photovoltage varies in the range of 2.0 to 2.6 V. We show that in the open-circuit condition, which is the usual case, the determination of radiative efficiency by measuring the PL intensity ratio of low-and high-temperature cannot be accurate, and the excitation intensity dependent PL cannot be solely intrinsic either. Both the absorption of incident laser and the carrier escape from the quantum well are bias-sensitive. By a simple and straightforward method, we determined that 51% of photogenerated carriers escaped in short-circuit condition.