Gills are one of the most primitive gas, solute exchange organs available in fishes. They facilitate exchange of gases, solutes and ions with a surrounding water medium through their functional unit called secondary lamella. These lamellae through their extraordinary morphometric features and peculiar arrangement in gills, achieve remarkable mass transport properties. Therefore, in the current study, modeling and simulation of convection-diffusion transport through a two dimensional model of secondary lamella and theoretical analysis of morphometric features of fish gills were carried out. Such study suggested an evolutionary conservation of parametric ratios across fishes of different weights. Further, we have also fabricated a thin microvascularised PDMS matrices mimicking secondary lamella by use of micro-technologies like electrospinning. In addition, we have also demonstrated the fluid flow by capillary action through these thin microvascularised PDMS matrices. Eventually, we also illustrated the application of these thin microvascularied PDMS matrices in solute exchange process under capillary flow conditions. Thus, our study suggested that fish gills have optimized parameteric ratios, at multiple length scale, throughout an evolution to achieve an organ with enhanced mass transport capabilities. Thus, these defined parametric ratios could be exploited to design and develop efficient, scaled-up gas/solute exchange microdevices. We also proposed an inexpensive and scalable method of fabrication of thin microvascularised polymer matrices and demonstrated its solute exchange capabilities under capillary flow conditions. Thus, mimicking the microstructures of secondary lamella will enable fabrication of microvascularised thin polymer systems through micro manufacturing technologies for potential applications in filtration, self-healing/cooling materials and bioengineering.