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In this paper we demonstrate high-baud generation and transmission of PDM-64QAM signals. The 64QAM signal is generated using one single in-phase/quadrature (I/Q) modulator driven with eight-level signals synthesized by all binary electrical inputs. With hard-decision forward error correction (HD-FEC), we first demonstrate 11.2-GBd and 22.4-GBd PDM-64QAM transmissions over 320-km standard single mode fiber (SSMF). Then we specifically introduce a long memory filter (LMF) and prove its effectiveness in reflection compensation both theoretically and experimentally. With the aid of soft-decision FEC (SD-FEC), optical pre-shaping, and LMF, we transmit a 41.4-GBd PDM-64QAM signal over 1200-km SSMF. Finally, using per-channel 41.6-GBd PDM-64QAM with SD-FEC, we successfully demonstrate 50-GHz-spaced, 8 × 499-Gb/s transmission over 720-km SSMF. This is the first demonstration of 400-Gb/s/ch WDM transmission on the 50-GHz ITU grid that uses a per-channel single-carrier scheme.