Materials featuring disordered structures often exhibit unique properties. Metal-organic frameworks (MOFs) are a class of hybrid materials composed of metal nodes and coordinating organic linkers[1]. Recently, there has been growing interests in MOFs with structural disorder, and the investigations of amorphous structures on surfaces[2]. Herein, we demonstrate a bottom-up method to construct molecular networks on metal surfaces with order-disorder transition by preparing two-component samples with different stoichiometric ratios of two organic molecule linkers sharing the same symmetry but differing in size[3]. We investigate the topological and electronic structures of the order/disorder molecular networks by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) under ultra-high vacuum (UHV). The results may advance our understanding of the formation mechanism and electronic behaviors characteristic of monolayer molecular networks with structural disorders, holding the potential to catalyze advancements in the design and application of new amorphous MOF materials with intriguing properties.[1] L. Dong, et al., Progress in Surface Science, 91, 101–135 (2016).[2] J. Fonseca, et al., Journal of Materials Chemistry A, 9.17, 10562-10611 (2021).[3] J. Lu, et al., ACS Nano, 17, 20, 20194–20202 (2023).