The visible plume, induced during pulsed-laser deposition (PLD) of epitaxial La0.5.jSr0.5 5CoO3/Ba0.4Sr0.6TiO3/La0.5Sr05CoO3/YBa2Cu3O7/YSZ heterostructures on silicon (100) wafers, was studied by optical-emission spectroscopy (OES). These films are suitable for the fabrication of ferroelectric capacitors and pyroelectric-sensor devices. A YAG laser, at 266 nm, is used for ablation. A collection lens transfers the PLD-plume emission into an optical fiber and onto a diffraction grating and a CCD array, for time-averaged spectroscopy from 410 to 640 nm. Plume emissions from ablated targets in the presence of an oxygen ambient, due to various atomic (Ba, Co, Cu, Sr, Ti, Y, Zr), ionic (Ba+, La+, Sr+, Y+), and a diatomic oxide (YO) species were identified. Emission intensity and evolution of ablated species are reported for distance away from the target surface, oxygen pressures, and laser fluences (1 to 4 J/cm2). The behavior of reactive-product species, especially YO for plumes from yttria-stabilized zirconia (YSZ) and YBCO targets, is discussed. This simple and inexpensive OES system is suitable for use as a plume-quality monitor on routine PLD film synthesis.