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This paper describes 100-Gb/s-class high-speed and large-capacity optical transmission technologies with focus on the modulation formats and high-speed optical/electrical devices. First, we review the recent progress of 100-Gb/s-class transmission technologies. We then discuss the transmission characteristics of several promising modulation formats with the line rate of 111 Gb/s. Next, we show the results of a 20.4-Tb/s transmission experiment using the 111-Gb/s CSRZ-DQPSK format and gain-flattened hybrid Raman/EDFAs.