A novel property existing in the stain-etching technique that eliminates the need for expensive etchant masks in the texturization process of silicon wafers was identified. Through the combination of grayscale lithography and stainetching methodologies, selective patterning of silicon with AR-P 3510 T, a positive-photoresist mask, was carried out. The etch area ratio was varied in nine different patterns of various feature sizes ranging from 400 to 1500 μm. The optical characteristics of the patterned substrates were determined from diffuse reflectance spectroscopy analysis, and the results were supported with finitedifference time-domain simulations. Complimenting the improvement in optical properties, the electrical losses in microwellpatterned photodetector devices have been reduced with an electro-optic optimum value of the surface enhancement factor, γ. The photodetecting efficiency of a selectively patterned microwell photodetector device exceeded the planar and black silicon photodetector devices with a considerable improvement in the pyrophototronic effect. This work suggests an alternative for black silicon optoelectronic devices providing a new route to fabricate selectively patterned substrates with an achieved detectivity 16-and 20-fold higher than black and planar silicon photodetector devices, respectively.