In this article, a methodology is presented regarding the design of a segment database for use with a time-domain speech synthesis system for the Greek language. The main issue of this process is the systematic generation of a corpus containing all possible instances of the segments for the specific language. Particular issues such as the phonetic coverage, the sentence selection as well as iterative evaluation techniques employing custom-built tools are discussed. The resulting corpus is characterised by a near-minimal size, provides a complete coverage of the Greek language and its distribution of phonemes is similar to that of natural corpora. A typical spoken acquisition procedure may then be performed, resulting in a segment database for use with a time-domain Greek synthesizer. The corpus creation procedure allows for the fine-tuning of the segment database's language-dependent characteristics and thus assists in the generation of high-quality text-to-speech synthesis.