Background: The physical attributes of residential neighborhoods, particularly the connectedness of streets and the proximity of destinations, can influence walking behaviors. To provide the evidence for public health advocacy on activity-friendly environments, large-scale studies in different countries are needed. Associations of neighborhood physical environments with adults' walking for transport and walking for recreation must be better understood. Method: Walking for transport and walking for recreation were assessed with a validated survey among 2650 adults recruited from neighborhoods in an Australian city between July 2003 and June 2004, with neighborhoods selected to have either high or low walkability, based on objective measures of connectedness and proximity derived from geographic information systems (GIS) databases. The study design was stratified by area-level socioeconomic status, while analyses controlled for participant age, gender, individual-level socioeconomic status, and reasons for neighborhood self-selection. Results: A strong independent positive association was found between weekly frequency of walking for transport and the objectively derived neighborhood walkability index. Preference for walkable neighborhoods moderated the relationship of walkability with weekly minutes, but not the frequency of walking for transport-walkability was related to higher frequency of transport walking, irrespective of neighborhood self-selection. There were no significant associations between environmental factors and walking for recreation. Conclusions: Associations of neighborhood walkability attributes with walking for transport were confirmed in Australia. They accounted for a modest but statistically significant proportion of the total variation of the relevant walking behavior. The physical environment attributes that make up the walkability index are potentially important candidate factors for future environmental and policy initiatives designed to increase physical activity.