Chain-of-Thought (CoT) and its variants have markedly advanced the reasoning abilities of Large Language Models (LLMs), yet their monolithic and auto-regressive architecture inherently conflates high-level strategic planning with low-level step-by-step execution, leading to computational inefficiency, limited exploration of reasoning paths, and reduced interpretability. To overcome these issues, we propose the Explore-Execute Chain ($E^2C$), a structured reasoning framework that decouples reasoning into two distinct phases: an exploratory phase that stochastically generates succinct high-level plans, followed by an execution phase that deterministically carries out the chosen plan. Our approach incorporates a two-stage training methodology, which combines Supervised Fine-Tuning (SFT) - augmented by a novel data generation algorithm enforcing strict plan adherence - with a subsequent Reinforcement Learning (RL) stage that capitalizes on the informativeness of exploration and reinforces the determinism of execution. This decomposition enables an efficient test-time scaling strategy: on AIME'2024, $E^2C$ Test Time Scaling reaches 58.1% accuracy using <10% of the decoding tokens required by comparable methods (e.g., Forest-of-Thought), sharply cutting self-consistency overhead. For cross-domain adaptation, our Exploration-Focused SFT (EF-SFT) fine-tunes with only 3.5% of the tokens used by standard SFT yet yields up to 14.5% higher accuracy than standard SFT on medical benchmarks, delivering state-of-the-art performance, strong generalization, and greater interpretability by separating planning from execution. The code and pre-trained models for the project are available at: https://github.com/yks23/Explore-Execute-Chain.git