Time‐resolved optical absorption spectroscopy techniques were used to study Ba, metastable Ba+, and YOabsorptionsin the laser‐produced plasma plume from a YBa2Cu3O7target. Results obtained indicate an initial explosive removal of material from the target surface followed by a subsequent evaporation process. Some YO is ejected from the target in molecular form, particularly at laser fluence <6 J/cm2, whilst additional YO is formed in subsequent reactions of Y with oxygen at the plasma plume edges. The formation of metastable Ba+(52D5/2) is also observed in the outer reactive layers of the plasma plume.