Old, digitized astronomical images taken before the human spacefaring age offer a rare glimpse of the sky before the era of artificial satellites. In this paper, we present the first optical searches for artificial objects with high specular reflections near the Earth. We follow the method proposed in Villarroel et al. and use a transient sample drawn from Solano et al. We use images from the First Palomar Sky Survey to search for multiple (within a plate exposure) transients that, in addition to being point-like, are aligned along a narrow band. We provide a shortlist of the most promising candidate alignments, including one with ∼3.9σ statistical significance. These aligned transients remain difficult to explain with known phenomena, even if rare optical ghosting producing point-like sources cannot be fully excluded at present. We explore remaining possibilities, including fast reflections from highly reflective objects in geosynchronous orbit, or emissions from artificial sources high above Earth's atmosphere. We also find a highly significant (∼22σ) deficit of POSS-I transients within Earth's shadow when compared with the theoretical hemispheric shadow coverage at 42,164 km altitude. The deficit is still present though at reduced significance (∼7.6σ) when a more realistic plate-based coverage is considered. This study should be viewed as an initial exploration into the potential of archival photographic surveys to reveal transient phenomena, and we hope it motivates more systematic searches across historical data sets.