The investment in hydrogen-refueling stations (HRS) is key to the development of a hydrogen economy. This paper focuses on the decision-making for potential investors faced with the thought-provoking question of when the optimal timing to invest in HRS is. To fill the gap that exists due to the fact that few studies explain why HRS investment timing is critical, we expound that earlier investment in HRS could induce the first mover advantages of the technology diffusion theory. Additionally, differently from the previous research that only considered that HRS investment is just made by one individual firm, we innovatively examine the HRS co-investment made by two different firms. Accordingly, we compare these two optional investment modes and determine which is better considering either independent investment or co-operative investment. We then explore how the optimal HRS investment timing could be figured out under conditions of uncertainty with the real options approach. Given the Chinese HRS case under the condition of demand uncertainty, the hydrogen demand required for triggering investment is viewed as the proxy for investment timing. Based on analytical and numerical results, we conclude that one-firm independent investment is better than two-firm cooperative investment to develop HRS, not only in terms of the earlier investment timing but also in terms of the attribute for dealing with the uncertainty. Finally, we offer recommendations including stabilizing the hydrogen demand for decreasing uncertainty, and accelerating firms’ innovation from both technological and strategic perspectives in order to ensure firms can make HRS investments on their own.