The organic light-emitting diode (OLED)-based sensing platform is gaining momentum due to unique attributes of the compact OLEDs that are used as excitation sources. This paper, however, points to issues related to this sensing platform that will affect many (bio)chemical sensing applications, in particular in photoluminescence (PL)-based sensors operated in the advantageous time domain, where pulsed OLEDs are utilized. The issues are related to the post-pulse electroluminescence (EL) profile, i.e., transient EL, which depends on the OLED materials and structure, and to the long-wavelength tail of the typically broad-band EL spectrum. Depending on materials and device structure, the transient EL may exhibit spikes peaking at ∼100–200 ns and μs-long tails. As shown, these interfere with the determination of PL decay times (that are related to analyte concentrations) of sensing elements. The results also indicate that the long-wavelength tail of the EL spectrum contributes to the interfering post-pulse μs-long EL tail. Hence, it is shown that the choice of OLED materials, the use of microcavity (μC) OLEDs with tunable, narrower EL bands, and the use of UV OLEDs alleviate these issues, resulting in more reliable data analysis. Furthermore, a 2-D uniform 2 μm-pitch microlens array that was previously used for improving light extraction from the OLEDs (J.-M. Park et al., Optics Express2011, 19, A786) is used for directional PL scattering toward the photodetector, which leads to a ∼2.1–3.8 fold enhancement of the PL signal. This behavior is shown for oxygen sensing, which is the basis for sensing of bioanalytes such as glucose, lactate, ethanol, cholesterol, and uric acid.