Respondent-driven sampling (RDS) is a form of chain-referral sampling, similar to snowball sampling, which was developed to reach hidden populations such as people who inject drugs (PWID). RDS is said to reach members of a hidden population that may not be accessible through other sampling methods. However, less attention has been paid as to whether there are segments of the population that are more likely to be missed by RDS. This study examined the ability of RDS to capture people with small injecting networks. A study of PWID, using RDS, was conducted in 2009 in Sydney, Australia. The size of participants' injecting networks was examined by recruitment chain and wave. Participants' injecting network characteristics were compared to those of participants from a separate pharmacy-based study. A logistic regression analysis was conducted to examine the characteristics independently associated with having small injecting networks, using the combined RDS and pharmacy-based samples. In comparison with the pharmacy-recruited participants, RDS participants were almost 80% less likely to have small injecting networks, after adjusting for other variables. RDS participants were also more likely to have their injecting networks form a larger proportion of those in their social networks, and to have acquaintances as part of their injecting networks. Compared to those with larger injecting networks, individuals with small injecting networks were equally likely to engage in receptive sharing of injecting equipment, but less likely to have had contact with prevention services. These findings suggest that those with small injecting networks are an important group to recruit, and that RDS is less likely to capture these individuals.