In this paper, a novel microalgal attached membrane photobioreactor based on the modified polyvinylidene difluoride (PVDF) / polyvinyl pyrrolidone (PVP) composite membrane for microalgae direct air carbon capture is developed and optimized. The Computational Fluid Dynamics (CFD) simulation, molecular dynamic study (MDS) and experimental study are adopted to investigate the synergy between light transmission and fluid flow, CO2 transmission mechanism inside the membrane and microalgae cells. The modified composite membrane is proposed and processed to improve the carbon sequestration rate of the microalgal attached membrane photobioreactor (AM-PBR). First, the synergy angle between the light transmission direction and fluid flow direction of the flat-plate photobioreactor (FP-PBR) is analyzed. To improve the synergy of light and fluid flow, the AM-PBR is proposed. Secondly, for the MDS part, the models of PVDF membrane and polytetrafluoroethylene (PTFE) membrane are developed. A three-layer simulation model is proposed to reveal the transmission mechanism of CO2 from the gas-liquid layer to the microalgae cell membrane layer. Several parameters including CO2 diffusion coefficient, CO2 concentration profile and velocity profile of CO2 are analyzed to compare the performance of different membranes and working conditions. Then, for verification of the simulation work, AM-PBR experiments are designed. To further enhance the CO2 transmission and microalgae attached performance, different PVDF/PVP composite membranes are assessed. The carbon sequestration rate of the modified membrane is improved according to the experiments. Finally, the novel microalgae membrane photobioreactor with the modified PVDF/PVP membrane is developed and the carbon sequestration rate of the PBR system is improved. The results showed that the best ratio for PVDF and PVP is 2:1 with 20 wt% solution, and with this modified membrane the carbon sequestration rate of the PVDF/PVP-based AM-PBR is 18.61% higher than the original PVDF-based AM-PBRs. The proposed novel AM-PBR is especially useful for low-concentration CO2 direct air carbon capture.