This study aims to examine associations between urban form factors generally, and street network configuration in particular, and walking for different purposes among children in Istanbul, Turkey. Parents of randomly selected students (ages 12–16) at 20 middle schools (N = 917) completed questionnaires about their socio-economic characteristics and the frequency of their children's walking for recreational and for transportation purposes in their neighbourhood during a typical day. The environment around 400 m of participants' homes was evaluated through GIS-based parcel-level land-use data and segment-based street connectivity measures calculated using space syntax techniques. Logistic geographically weighted regression models were estimated to measure the desired associations while adjusting for socio-economic characteristics. Results demonstrate a marginal association between urban form measures and walking behaviour but only in certain peripheral parts of the city. More importantly, increased directional accessibility, which identifies the extent to which more street length is accessible within few direction changes, is associated with higher odds of recreational walking in particular areas where a strong differentiation between scales of street connectivity structure is evident such as a supergrid of primary roads with inserted organic local streets. In addition, children residing in neighbourhoods with reduced residential density and increased commercial and recreational activities are more likely to walk for transportation purposes. The findings of this study demonstrate that the one-size-fits-all approach may not effectively encourage walking. Urban areas tend to have varying qualities that need to be handled uniquely, and therefore targeted rather than blanket interventions regarding the design of neighbourhoods around schools and homes may be beneficial in supporting walking behaviour of children.