NaFeAs are in progress. Anisotropy of electronic transport properties have also been studied and the results are shown in Fig.2 (b) and (c). The similar behavior of field on the transition is observed. When the magnetic field is applied within ab plane, the transition is less affected than the situation when the field is applied along the c axis. The corresponding values are − dH c 2 /dT | T$_{c}$ =6.0 T/K for H ‖ ab and − dH c 2 /dT | T$_{c}$ =3.4 T/K for H ‖ c . Taking 33 K as Tc and using WHH formula, we get the corresponding upper critical fields as high as H ab c $_{2}$=137 T and H c c $_{2}$=77 T. Such high critical fields and low anisotropy ratio (137/77=1.78) are comparable to other 122 system and may have the potential for future applications in the superconducting devices. Recently, Chong et al. summarized the results of high field study on 122 and 111 samples and concluded that the hole-doped system have higher upper critical fields > 100 T compared to the electron-doped system, while those of strain or pressure induced superconductvity have similar upper critical fields as in the electron-doped system.[31] They did the measurements on single crystalline BaFe 2 As 1 . 36 P 0 . 64 (Tc=31 K) and estimated the upper critical fields as H ab c $_{2}$=77 T and H c c $_{2}$=36 T. Our results of upper critical fields with H ab c $_{2}$=137 T and H c c $_{2}$=77 T are the largest among the 111 and 122 systems except for those in hole-doped cases and it is the first exception of samples with upper critical field > 100 T which is non-hole-doped system. Previous high magnetic field experiments on (Ba,K)Fe 2 As 2 show nearly isotropic superconductivity in that system[32] and later the same conclusion is drawn by other high magnetic field experiments on Ba(Fe,Co) 2 As 2 .[33, 34] So, it is necessary to do the high magnetic field experiments in the 111 system and the work is in progress. To summarize, we have grown the high quality single crystals of NaFeAs with Co- and P-doping. We find that the superconductivity occurs at ambient pressure with Tc up to 33 K in NaFeAs 0 . 8 P 0 . 2 . We emphasized that the value of Tc is the highest in 111 system and in all other isoelectronic element substituted 122 or 1111 system. The upper critical fields are estimated high up to 77 T with H ‖ c and 137 T with H ‖ ab for NaFeAs 0 . 8 P 0 . 2 , which are also the highest in 122 and 111 systems except for those in hole-doped cases. We believe that these results provide important information for establishing a theory to understand the superconductivity in the iron-based superconductor. The work is supported by the National Science Foundation of China and the 973 project 7