Objective: To study the biocompatibility of poly (hydroxybutyrate-hydroxyvalerate) (PHBV) modified by low temperature plasma with NH3, CO2, and O2 with canine Endothelial cells (ECs) and provide the better materials for blood vessel tissue engineering via surface modification. Methods: PHBV was modified by low temperature plasma with NH3, CO2, and O2, for 0, 5, 10, 20, and 30 min respectively, PHBV not modified was used as control group. The contact angle was measured. X-ray photoelectron spectroscopy was used to detect the surface elements. Canine endothelial cells (ECs) were cultured on the surface of PHBV and were stained with fluorescence isothiocyanate (FITC). Their morphological characteristics were observed with fluorescence microscopy, and the cell proliferation was detected with MTY assay. Results: The surface contents of carbon of the PHBV modified by low temperature plasma with O2 and CO2 were 63.75% and 69.72%, both lower than that before modification (77.97%). The surface contents of oxygen of the PHBV modified by low temperature plasma with O2 and CO2 were 30.72% and 28.48%, both higher than that before modification (21.74%). The surface content of nitrogen of the PHBV modified by low temperature plasma with NH3 was 3.25%, remarkably higher than that before modification (0). The contact angles of different modification groups, especially those of the 5 min groups, were all significantly smaller than that of the unmodified group (P < 0.05 or P < 0.01). Compared with the control group, the cytocompatibility was better in the low temperature plasma modified groups. Conclusion: The surface of PHBV modified by low temperature plasma with NH3, CO2, and O2 has active groups and good biocompatibility, so the surface modification of low temperature plasma with NH3, CO2, and O2 can be a kind of effective method for the tissue engineering blood vessel.