TBM concrete segment requires a higher level of material properties compared to general concrete structures due to difficulties in maintenance and uncertainty in ground conditions. In this regard, recently, as one of the methods to achieve enhancement effect on concrete strength, many researchers have been focusing on adding CNTs to concrete mixture. However, even CNTs do not compensate the weakness that concrete exhibits brittle behavior after cracking. Separately, over the past few decades, a number of studies have been conducted on fiber reinforced concrete which exhibits ductile behavior due to fibers bridging cracks. However, only limited studies have been conducted to employ the advantages of the both materials together. In this study, an experimental program has been conducted to investigate the effect of CNTs on the workability and the compressive behavior of PVA-ECC which exhibits ductile tensile behavior with well-distributed cracks even without a conventional rebar. In addition to the compression test, SEM analysis has been also conducted for detailed investigation in the microstructure. The variable was the CNTs mix ratio, which were set to 0.00, 0.25, and 0.50 wt.% to the binding materials. It was observed though the test results that as the CNTs mix ratio increased, the workability considerably decreased with the reduced slump and slump flow. From the compression test results, it was also investigated that the compressive behavior was improved since the compressive strength, the strain corresponding to the compressive strength, and the modulus of elasticity increased with an increase of CNTs mix ratio. The contents of this paper will be useful for relevant research areas such as fiber reinforced concrete with CNTs which might be applied for high performance TMB concrete segments.