Identification of viable vat dye candidates of a trichromatic series (compatible red, yellow and blue colorants) plus an orange based on the developed single-stage acid leuco vat dyeing process for unmodified polypropylene (PP) flat woven fabrics has been achieved with adequate fastness properties to washing, crocking and dry-cleaning: C. I. Vats Orange 1, Yellow 2 and Red 1 have been certified, whereas Vat Blue 6 is a marginal candidate. Vat Blue 1 has been demonstrated to be a viable colorant for dyeing of PP fiber as a single colorant. Molecular dynamics simulation and solubility parameter (SP) approaches have been utilized to screen the potential vat dye candidates for generic PP coloration. Experimental K/S results have exhibited good correlation with the predicted mixing energy of acid leuco vat dyes-PP fiber and the calculated dyes' SP's. The low SP/mixing energy acid leuco vat dyes (e.g., C. I. Vat Red 1) have shown better color-yield/fastness properties than the high SP/mixing energy vat dyes (e.g., C. I. Vat Brown 1), exhibiting that increasing difference of SP between the vat dye and the PP fiber, coupled with a higher mixing energy of dye-PP blend, resulted in decreased interactions between the two. For example, C.I. Vat Brown 1 with its high SP and calculated mixing energy with PP gave least color yield than the certified vat dyes, all with lower SP's and mixing energies. Cross-section micrographs of the dyed fibers revealed the absence of "ring-dyeing". Experimentally determined kinetic parameters such as affinity of dyeing and heat of dyeing quantified the presence of interaction between acid leuco vat dyes and PP fiber. Tensile test and X-ray crystallinity results have confirmed that dyeing process did not alter the tensile strength and modulus of the dyed PP textiles significantly. PP Fabrics dyed with simulated continuous dyeing processes (pad-steam and pad-dry heat) demonstrated good color yields and levelness with adequate fastness to crocking, washing and dry cleaning.