Using time- and angle-resolved photoemission spectroscopy, we investigate the photoexcited electron dynamics in a prototypical charge density wave (CDW) material, Rb 0.3 MoO 3 . We observe a pronounced slow relaxation component within the CDW-gap energies. This anomalously slow dynamics is independent of the wave number, and cannot be explained by the presence of impurities. We propose that phase-coherent domains are temporarily established after a transient closure of the CDW gap, and that the intragap excitations are attributed to relaxation of the domain boundaries. • Photoexcited electron dynamics are investigated in a prototypical CDW material. • Anomalously long-lived component is observed. • It is independent of the wave number and not affected by impurities. • The slow dynamics are attributed to relaxation of the coherent domain boundaries.

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