Structure and stability of cadmium arachidate (CdA) Langmuir-Blodgett (LB) films on homogeneous (i.e., OH-, H-passivated Si(001) substrates) and heterogeneous (i.e., Br-passivated Si(001) substrates) surfaces were studied using x-ray reflectivity and atomic force microscopy techniques and compared with those of nickel arachidate (NiA) LB films. While on OH-passivated Si, asymmetric monolayer (AML) structure starts to grow, on H-passivated Si, symmetric monolayer (SML) of CdA forms, although for both the films, pinhole type defects are present as usual. However, on heterogeneous Br-passivated Si substrates, combination of AML, SML, shifted SML and SML on top of AML (i.e., AML/SML), all types of structures are found to grow in such a way that, due to the variation of heights in the out-of-plane direction, ring-shaped in-plane nanopatterns of CdA molecules are generated. Probably due to stronger head-head interactions and higher metal ioncarboxylic ligand bond-strength for CdA molecules compared to NiA, easy flipping of SML on top of another preformed SML, i.e., SML/SML structure formation was not possible and as a result a wave-like modulation is observed for CdA film on such heterogeneous substrate. Presence of hydrophilic/hydrophobic interfacial stress on heterogeneous substrate thus modifies the deposited molecular structure so that the top surface morphology for CdA film is similar with monolayer buckling while that for NiA film it is similar with monolayer collapse.