Multi-core systems-on-chip are becoming state-of-the-art. Therefore, there is a need for a fast and energy-efficient interconnect to take full advantage of the computational capabilities. Integration of silicon photonics with a traditional electrical interconnect in a Network-on-Chip (NoC) proposes a promising solution for overcoming the scalability issues of electrical interconnect. In this article, we derive and evaluate prediction modeling techniques for the design space exploration (DSE) of application-specific communication architectures for an Optical Network-on-Chip (ONoC). Our proposed model accurately predicts network packet latency, contention delay, and the static and dynamic energy consumption of the network. This work specifically addresses the challenge of accurately estimating performance metrics of the entire design space without having to perform time-consuming and computationally intensive exhaustive simulations. The proposed technique, based on machine learning (ML), can build accurate prediction models using only 10% to 50% (best case and worst case) of the entire design space. The accuracy, expressed as R 2 (Coefficient of Determination) is 0.99901, 0.99967, 0.99996, and 0.99999 for network packet latency, contention delay, static energy consumption, and dynamic energy consumption, respectively, in six different benchmarks from the Splash-2 benchmark suite, chosen among 6 different machine learning prediction models.