Electroencephalography (EEG) signals provide a promising and involuntary reflection of brain activity related to emotional states, offering significant advantages over behavioral cues like facial expressions. However, EEG signals are often noisy, affected by artifacts, and vary across individuals, complicating emotion recognition. While multimodal approaches have used Peripheral Physiological Signals (PPS) like GSR to complement EEG, they often overlook the dynamic synchronization and consistent semantics between the modalities. Additionally, the temporal dynamics of emotional fluctuations across different time resolutions in PPS remain underexplored. To address these challenges, we propose PhysioSync, a novel pre-training framework leveraging temporal and cross-modal contrastive learning, inspired by physiological synchronization phenomena. PhysioSync incorporates Cross-Modal Consistency Alignment (CM-CA) to model dynamic relationships between EEG and complementary PPS, enabling emotion-related synchronizations across modalities. Besides, it introduces Long- and Short-Term Temporal Contrastive Learning (LS-TCL) to capture emotional synchronization at different temporal resolutions within modalities. After pre-training, cross-resolution and cross-modal features are hierarchically fused and fine-tuned to enhance emotion recognition. Experiments on DEAP and DREAMER datasets demonstrate PhysioSync's advanced performance under uni-modal and cross-modal conditions, highlighting its effectiveness for EEG-centered emotion recognition.