Purpose. To determine the structure–function relationship between cluster mean defect (MD) offered by standard automated perimetry and corresponding sector peripapillary retinal nerve fiber layer thickness (pRNFLT) measured with optical coherence tomography (OCT) in primary open angle glaucoma (POAG). Method. 39 healthy eyes (control group), 43 early POAG eyes (global MD ≤ 6 dB, early group), 30 moderate POAG eyes (global MD between 6 and 12 dB, moderate group), and 53 advanced POAG eyes (global MD > 12 dB, advanced group) underwent visual field (VF) examination with Octopus perimeter (dynamic strategy/G2 pattern) and peripapillary retinal nerve fiber layer thickness measurements with RTVue-100 FD-OCT. Spearman analysis was used to investigate the correlation between cluster MDs provided by Octopus perimeter and corresponding sector pRNFLT for the total sample and each subgroup, respectively. Then, linear (y = a+ bx) and curvilinear (quadratic, y = a+bx + cx2) regression analyses were employed to investigate the model for the cluster MD-sector pRNFLT pair with significant correlation. The strength of the relationship was characterized with correlation coefficient (ρ) and coefficient of determination (R2). For the cluster–sector pair that could be fitted by both models, Wilcoxon signed rank test of absolute residuals was used to compare the goodness of fit. Results. Correlation between cluster MDs and corresponding sector pRNFLT was significant for all clusters in the total sample (ρ values: −0.572 to 0.832,
P
<
0.001
) and in the POAG group (ρ values: −0.551 to −0.777,
P
<
0.001
). The highest ρ values were found for cluster-sector pair 9 and pair 3, respectively. The curvilinear (quadratic) model provided better fit for all 10 cluster-sector pairs in the total sample (R2 values: 0.431–0.687,
P
<
0.001
) and in the POAG group (R2 values: 0.364–0.594,
P
<
0.01
). The highest R2 values were found also for cluster–sector pair 9 and pair 3, respectively. In the control group, no significant correlation was found for any cluster–sector pair (
P
>
0.01
). In the early group, correlation was significant for cluster–sector pairs 3, 8, and 9 (ρ values: −0.449, −0.627, and −0.815, resp.,
P
<
0.01
). In the moderate group, correlation was significant for pairs 2, 3, 8, and 9 (ρ values: −0.703, −0.556, −0.680, and −0.637, resp.,
P
<
0.01
). In the advanced group, correlation was significant (
P
<
0.01
) for all 10 pairs (ρ values: −0.395 to −0.699,
P
<
0.001
) except for pairs 2, 3, and 8, and the highest ρ value was found for pair 1. For all cluster–sector pairs with significant correlation in the early, moderate, and advanced groups, only linear model could be fitted (
P
<
0.01
), except for pair 9 in the early group and pair 5 in the advanced group. Conclusions. Cluster MD of the Octopus visual field showed significant moderate-to-strong negative correlation and curvilinear (quadratic) relationship with the corresponding sector pRNFLT for POAG. This type of regional structure–function relationship varied according to the severity of POAG, and at each stage, the significantly correlated cluster–sector pairs mainly showed linear relationship. The results could provide guidance for better utilization of this regional structure–function method in the management of different stages of POAG.